Organometallics 1995,14, 4549-4558
4549
Synthesis and Structures of Trans-ChelatingChiral Diphosphine Ligands Bearing Aromatic P-Substituents, (S,S)-(R,R)-and ( R s ) (S,S)-2,2”-Bis[1 (diary1phosphino)ethyll 1,1”-biferrocenes (ArylTRAPs),and Their Transition Metal Complexes
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-
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Masaya Sawamura,*>+Hitoshi Hamashima, Masanobu Sugawara, Ryoichi Kuwano, and Yoshihiko Ito* Department of Synthetic Chemistry and Biological Chemistry, Kyoto University, Kyoto 606-01, Japan Received March 21, 1995@ The trans-chelating chiral phosphine ligand (S,S)-(R,R)-2,2”-bis[l-(diphenylphosphino~ethyl]-1,l”-biferrocene (la, abbreviated to PhTRAP) was synthesized from (S)-l-(NJVdimethy1amino)ethylferrocene(2) in four steps in 51% overall yield. (R,RR)-(S,S)-PhTRAP and other arylTRAP derivatives (lb, AnisTRAP; IC, C1-PhTRAP, Id, FurTRAP; le, TolPhTRAP) were synthesized in a similar manner. Through-space 31P-31Pspin couplings were observed indirectly in the IH and 13C{lH}NMR spectra of la-e and directly in the 31P{1H} NMR spectrum of asymmetrical TRAP le, indicating that the two phosphorus atoms of the ligands are in close proximity. Results of NOE experiments showed that PhTRAP is a fairly rigid molecule and in a conformation favorable for trans-chelation. As square planar transition metal complexes bearing arylTRAPs as trans-chelating ligands, trans-[PdxZ{(27,s)(R,R)-PhTRAP}l (7, X = Br; 8, X = I; 9, X = Cl), trans-[PtC12{(R,RR>-(S,S)-PhTRAP)3 (lo), t r u n s - [ P t C l ~ { ( S , S ) - ( ~ , R )(ll), - l e } ]trans-[IrC1(CO){(S,S)-(R,R)-PhTRAP}l (12),trans-[RhCl(CO){(S,S)-(R,R)-PhTRAP}] (13), and trans-[RhCl(CO){(S,S)-(R,R)-FurT~}I(14) were prepared and fully characterized. X-ray crystal structures were determined for the palladium complex 7 and the rhodium complex 14.
Introduction Asymmetric synthesis catalyzed by chiral phosphinetransition metal complexes is an area of research that has been attracting a great deal of interest due t o its high efficiency for the synthesis of optically active compounds.l Recent progress in this area has been prompted mostly by the molecular design and synthesis of new effective chiral phosphine ligands. Earlier, we reported the synthesis of trans-chelating chiral diphosphine, (R~)-(S,S)-2,2”-bis[1-(diphenylphosphino)ethyll1,l”-biferrocene (la, abbreviated to PhTRAP), which possesses planar chiralities as well as stereogenic centers, and this ligand proved to coordinate to palladium and platinum in bidentate trans-chelation m a n n e ~ - . ~High - ~ chiral recognition ability of this ligand was demonstrated in the Rh-catalyzed asymmetric + Present address: Department of Chemistry, School of Science, The University of Tokyo, Tokyo 113,Japan. Abstract published in Advance ACS Abstracts, September 1, 1995. (1)For reviews, see: (a) Ojima, I., Ed. Catalytic Asymmetric Synthesis; VCH Publishers: New York, 1993.(b) Ojima, I.; Clos, N.; Bastos, C. Tetrahedron 1989, 45, 6901.(c) Noyori, R.;Kitamura, M. In Modern Synthetic Methods; Scheffold, R., Ed.; Springer-Verlag: Berlin, 1989;Vol. 5, p 115. (2) Sawamura, M.; Hamashima, H.; Ito, Y. Tetrahedron: Asymmetry 1991,2,593. (3)For terdentate chiral phosphine ligands spanning trans-positions, see: (a)Brown, J. M.; Chaloner, P. A.; Descotes, G.; Glaser, R.; Lafont, D.; Sinou, D. J.Chem. Soc., Chem. Commun. 1979,611.(b) Descotes, G.; Lafont, D.; Sinou, D.; Brown, J. M.; Chaloner, P. A.; Parker, D. Nouu. J. Chim. 1981,5,167.(c) Burk, M. J.;Feaster, J . E.; Harlow, R. L. Tetrahedron: Asymmetry 1991,2,569.(d) Gorla, F.; Venanzi, L. M. Organometallics 1994,13,43.( e )Gorla, F.; Togni, A,; Venanzi, L. M.; Albinati, A.; Lianza, F. Organometallics 1994,13,1607. @
0276-7333/95/2314-4549$09.0QIO
Michael reaction of 2-cyan0propionates.~Later, TRAP derivatives bearing flexible alkyl substituents on phosphorus atoms (alkylTRAPs)were prepared, and some of those were shown to be effective chiral ligands for the Rh-catalyzed asymmetric hydrosilylation of simple ketones.6 In this paper we wish to report the syntheses and structures of several TRAP derivatives bearing aromatic substituents on phosphorus atoms (la-e, arylTRAPs) and their transition metal complexes.
(S,S)-(R,R)-la-e
(R,R)-(S,S)-la-e
a: Ar = At‘ = Ph (PhTRAP) b: Ar = At‘ = pMeO-Ph (AnisTRAP) c: Ar = Ar’ = pCI-Ph (CI-PhTRAP) d: Ar = At‘ = 2-Fulyl (FurTRAP) e: Ar = Ph, At‘ = pTol (Tot-PhTRAP)
(4)For an achiral trans-chelating diphosphine, see: (a)DeStefano, N. J.; Johnson, D. K.; Venanzi, L. M. Angew. Chem., Int. Ed. EngZ. 1974,13,133.(b)Burgi, H.-B.; Murray-Rust, J.; Camalli, M.; Caruso, F.; Venanzi, L. M. Helu. Chim. Acta 1989,72, 1293 and references cited therein. (5)Sawamura, M.; Hamashima, H.; Ito, Y. J.Am. Chem. SOC.1992, 114, 8295. (b) Sawamura, M.; Hamashima, H.; Ito, Y. Tetrahedron 1994,50,4439. (6)Sawamura, M.; Kuwano, R.; Ito, Y. Angew. Chem.,Int. Ed. Engl. 1994,33,111.
0 1995 American Chemical Society
4550 Organometallics, Vol. 14, No. 10,1995
Sawamura et al.
Scheme 1 &Me2 Fe
Me
Fe
.,, Me
1. Me1 2. LiP(0)Ar2 c
FI
(s)-(R)-4: x = I (q-5: X - H
(S,S)-(R,R)-B
a: Ar = Ph b: Ar = pMeO-Ph c: Ar = pCI-Ph
c: Ar = At = pCI-Ph
d: Ar 2-Fury1 e: Ar = pTol
d: Ar = At' = 2-Fury1 e: Ar = Ph, A t = pTol
-
a: A r = A t = P h b: Ar = A t = pMeO-Ph
Results and Discussion Synthesis of ArylTRAPs. The synthesis of (S,S)(R,R)-arylTRAPsbearing different aromatic P-substituents is outlined in Scheme 1. For the synthesis of (S,S)-(R,R)-PhTRAP (la), optically pure (S)-l-(iVJVdimethy1amino)ethylferrocene (2)7was converted into iodoferrocene derivative (S)-(R)-3via diastereoselective ortholithiation with sec-BuLi and subsequent reaction = 42:11.8 The crude mixture with iodine [(S)-(R)-:(S)-(S)of 3 was treated with Me1 and was then subjected to the substitution reaction with lithium diphenylphosphinite in refluxing MeCN to give a mixture of phosphine oxides (S)-(R)-4aand (S)-Sa. The nucleophilic substitution reaction proceeded with complete retention of configuration a t the stereogenic s enter.^ The homocoupling O f 4a was best performed with activated copper powderlo a t 130 "C (neat), producing Cz-symmetric biferrocene (S,S)-(R,R)-Ga.Finally, reduction of the phosphine oxide with HSiC13/Et3N11 afforded (S,S)(R,R)-PhTRAP (la) as an orange powder. Thus, the chiral ligand was synthesized in four steps in 51% overall yield starting with (S)-1-(NJV-dimethylamino)ethylferrocene (2),7 which is easily obtainable in large quantities in optically pure form for both enantiomers. The crude compounds 3 and 4a were used for any further synthetic transformations. (R,R)-(S,S)PhTRAP and other arylTRAP derivatives, which have p-methoxyphenyl (lb,AnisTRAP), p-chlorophenyl (IC, Cl-PhTRAp), or 2-fury1 (Id, FuflRAP) groups on the phosphorus atoms, were synthesized in a similar man(7) Marquarding, D.; Klusacek, H.; Gokel, G.; Hoffmann, P.; Ugi, I. J . Am. Chem. Soc. 1970.92.5389. (8)Watanabe, M.; Ar'aki,' S.; Butsugan, Y.; Uemura, M. J . Org. Chem. 1991.56.2218. (9)(a) Goke1,'G. W.; Marquarding, D.; Ugi,I. J . Org. Chem. 1972, 37, 3052. (b) Hayashi, T.;Mise, T.; Fukushima, M.; Kagotani, M.; Nagashima, N.; Hamada, Y.; Matsumoto, A.; Kawakami, S.; Konishi, M.; Kamamoto, K.; Kumada, M. Bull. Chem. SOC.Jpn. 1980,53,1138. (10)Fuson, R. C.; Cleveland, E. A. Organic Syntheses; Wiley: New York, 1955;Collective Vol. 3,p 339. (11)Naumann, K.; Zon, G.; Mislow, K. J . Am. Chem. SOC.l969,91, 7012.
ner. For the synthesis of unsymmetrical TRAP le, an equimolar mixture of 4a and 4e was subjected to the copper-promoted coupling. HPLC separation of three statistically formed coupling products gave pure 6e. Structure of A r y l W s . Full assignment o€the lH (400 MHz) and 13C{lH} (100 MHz) NMR spectra of (S,S)-(R,R)-PhTRAP(la)in CDC13 has been done with the aid of lH{lH} NOE (Table 1, Figure 11, HETCOR, HMBC, and 13C INADEQUATE (see supporting information for details of the assignment). Reflecting the CZsymmetry of the molecule, each 2-[l-(diphenylphosphino)ethyllferroceny1unit is equivalent in both lH and l3C{IH}NMR spectra. In the 31P{1H}NMR spectra (81 MHz, 85% of la in CDC13 the resonance for two phosphorus atoms appeared at 6 2.19 ppm as a broad singlet. It is noteworthy that the resonance for the side chain a-methyl protons does not appear as a simple double doublet and that most of the 13Cresonances split into multiplet. Aromatic region of the 13C{lH} NMR is shown in Figure 2. These data suggest that there exists a through-space 31P-31Pspin coupling due to the close proximity of the two phosphorus atoms.12J3The 31P31Pspin coupling was directly observed in the 31P{1H} NMR spectrum of unsymmetrical TRAP le, where the resonances for two phosphorus atoms appeared separately at 6 0.4 and 2.6 ppm as a set of doublets with a 31P-31P coupling constant of 22.0 Hz. Since the two phosphorus atoms are connected through seven a-bonds, spin coupling through the bonds should not be taken into consideration. Such close proximity seems to be possible only for the conformation where the lone pairs of the two phosphorus atoms converge in the cavity created by four aromatic P-substituents and biferrocene backbone as depicted in Figure 1. The NOE technique was used not only for the assignment of the lH NMR spectrum of (S,S)-(R,R)-PhTRAP (la) but also for the conformational study in solution. Observed NOEs are summarized in Table 1. Figure 1 shows the view of the ligand in a conformation which is consistent with the NOEs. Selected NOEs are also shown in Figure 1. The irradiation of methyl protons (HM~) gave rise to large NOE enhancements at ferrocenyl protons fi (18%)and at protons on unsubstituted Cp rings Hc, (18%)together with a weak enhancement a t €&i (4%). On the other hand, the irradiation of Ha caused no NOE at 6 while giving a large NOE enhancement at €&i (12%)and a weak enhancement at Hc, (3%). Upon irradiation of Hs was obtained an NOE of 7% a t Ha together with a large NOE at Hc, (15%). The NOEs between the ferrocenyl protons €&i and side chain protons (Ha, HMJ should be attributed to the NOEs caused by the relaxation toward the other 241(diphenylphosphino)ethyl]ferrocenyl components. The large NOE from & to HQ,is also explained by considering the contribution of relaxation toward the Hc, of the other ferrocenyl moiety. These NOEs described above and all other NOEs summarized in Table 1 are in good agreement with the conformation predicted in an earlier paper.2 (12)Redfield, D.A.;Cary, L. W.; Nelson, J. H. Inorg. Chem. 1975, 14,50. (13)For through-space 31P-31P coupling, see: (a) Haenel, M. W.; Fieseler, H.; Jakubik, D.; Gabor, B.; Goddard, R.; Krtiger, C. Tetrahedron Lett. 1993,34, 2107.For through-space 19F-19F coupling, see: (b) Mallory, F. B.; Mallory, C. W.; Ricker, W. M. J . Org. Chem. 1985, 50, 457.
Organometallics, Vol. 14,No.10, 1995 4551
Trandhelating Chiral Diphosphine Ligands
Table 1. 'H{'H} NOEs of (S,,S)-(R,ZZ)-PhTRAp(la) in CDClp enhancement, %b irradiated position
H M(6 ~ 1.35) H a (6 3.49) H3 (6 3.79) & (6 4.12) H.5 (6 4.55) a
H4
H5
HCP
Hph
(6 3.49)
H3 (6 3.79)
(6 4.12)
(6 4.55)
(6 4.29)
(6 7.05-7.40)
+15.9
f17.6
-1.8 -0.8 $12.8
+3.5 +11.9 -0.5 +8.6
+17.6 +3.4 +3.7
+15.9 +23.7, -3.4 f1.6
Ha
HM~ (6 1.35) +7.6 +4.8
c C
C
c
c
+6.9
+11.4 -1.0
c c
C
+12.9
+14.9
The experiment was performed a t 200 MHz at ambient temperature. Reduced values to one irradiated proton.
NOE was not observed.
Ph
/r\
\p-Ph Q 1.P
140
138
136
i34
132
130
I28
126
Figure 3. 13C{lH}NMR (100 MHz) spectrum of trans[PdBrz{(S,S)-(R~R)-PhTRAP}l(7) in CDCb (phenylregion).
Figure 1. Selected lH{lH} NOEs (% enhancement) of (S,S)-(R,R)-PhTFUP(la) in CDC13.
b
Ala
Figure 2. l3C{lH) NMR (100 MHz) spectrum of (S,S)(R,R)-PhTRAP(la) in CDCl3 (phenyl region). Although efforts to obtain an X-ray crystal structure were unsuccessful, results of the NOE study and the existence of through-space 31P-31Pspin coupling indicate that arylTRAPs are fairly rigid molecules and in a conformation favorable for trans-chelation. Palladium Complexes. Reaction of (S,S)-(R$)PhTRAP with PdBr2 in CHzClz at room temperature formed truns-[PdBrz{(S,S)-(R$)-PhTRAP}l (7) exclusively, Two 24 1-(dipheny1phosphino)ethyllferrocenyl units were equivalent in both 'H (400 MHz) and 13C{'H} (100 MHz) NMR spectra. The 31P{1H}NMR (81 MHz) showed a singlet peak at 6 29.9 ppm. In the 13C{ lH} NMR spectrum, phosphorus-coupled resonances split into a 1:2:1 triplet (Figure 3). Such a triplet could be observed when a 13Cnucleus and two 31Pnuclei form an AXX' spin system and the two 31P nuclei couple to each other with a large coupling constant.12 Although the 31P-31Pcoupling constant cannot be directly determined, the characteristic splitting of 13C{lH} NMR spectrum clearly indicates that the two chemically equivalent phosphorus atoms are bound t o palladium in a trans manner. truns-[PdI2(PhTRAP)I(8)and trans[PdC12(PhTRAP)I(9) were similarly prepared from PdI2 and PdC12(MeCN)2, respectively. Trans-chelation of P h T W was confirmed by the X-ray crystal structure analysis of trUns-PdBn[(S,S)(R,R)-PhTW] (7). An ORTEP drawing with atom-
labeling scheme is shown in Figure 4. Bond distances and angles are given in Table 2. The environment of the Pd atom is described as slightly distorted square planar with two trans phosphorus atoms and two trans bromine atoms. Bond angles P(l)-Pd(l)-P(P) and Br(l)-Pd(l)-Br(2) are 163.6(1) and 167.44(8)", respectively. The bond distances of two Pd-P bonds and two Pd-Br bonds are normal. Two phosphorus atoms are located in the exo region of ferrocene, dihedral angles P(l)-C(l)-C(3)-C(7) and P(2)-C(13)-C(15)-C(19) being 92( l)and 100(l)", respectively. The angle between the least-squares planes through the two linked Cp rings (C3-C7, C15-Cl9) is 121.4". Another view normal t o the virtual square plane is shown in Figure 5, where the deviation from C2 symmetry is well visualized. For example, the orientation of four Ph groups is asymmetrical, and the o-bonds connecting the two ferrocene units are not positioned on the imaginary C2 axis. Such a deviation seems to be caused by the
Suwamura et al.
4552 Organometallics, Vol. 14, No. 10, 1995
n
C41
w Figure 5. View of trans-[PdBrz{(S,S)-(R~))-PhTRAP}l(7) normal to the virtual square plane (hydrogen atoms are omitted for clarity).
Table 2. Selected Bond Lengths (A)and Angles (deg) of 7 __ Pd(1)-Br(1) Pd(l)-P(l) P(1)-C(1) P(l)-C(31) P(2)-C(37) BdlFPd(lFBr(2) Br( l)-Pd(l)-P(2) Br(3)-Pd(l)-P(2) Pd(l)-P(l)-C(l) Pd(l)-P(l)-C(31) C(l)-P(l)-C(31) Pd(l)-P(2)-C(13) Pd(l)-P(2)-C(43) C(13)-P(2)-C(43)
Bond Lengths (A) 2.414(2) Pd(l)-Br(2) 2.327(4) Pd(l)-P(2) 1.87(1) P(l)-C(25) 1.85(2) P(2)-C(13) 1.83(2) P(2)-C(43)
Angles (deg) 167.44(8) Br(l)-Pd(l)-P(l) Br(2)-Pd(l)-P(l) 96.5( 1) P(l)-Pd(l)--P(2) 85.4(1) Pd(l)-P(l)-C(25) 106.4(5) C(l)-P(l)-C(25) 116.5(5) C(25)-P(l)-C(31) 110.9(7) Pd(l)-P(2)-C(37) 104.8(5) C(13)-P(2)-C(37) 111.8(5) C(37)-P(2)-C(43) 108.4(7)
2.432(2) 2.341(4) 1.81(1) 1.86(1) 1.81(2) 93.0(1) 88.3(1) 163.6(1) 117.5(5) 101.4(7) 103.1(7) 125.5(5) 104.3(7) 101.1(7)
steric bulkiness of Ph groups. Two bromine atoms on Pd are deeply buried in the chiral cavities created by the biferrocenyl backbone and Ph groups, suggesting a high degree of chiral recognition ability of P h T W as a chiral ligand for catalytic asymmetric synthesis. Platinum Complexes. The reaction of (R,R)-(S,S)PhTRAP (la) with 1 equiv of PtC12(MeCN)2 in CHCl3 at 40 "C for 12 h gave two platinum species in a ratio of 20:l. The 31P{1H}NMR spectrum (CDCl3,85% of the major product (6 21.41) was accompanied by its lg5Ptsatellite with a J195pt-31~value of 2612 Hz, indicating the trans geometry of two phosphorus atoms.14 On the other hand, the minor product was deduced to have a cis geometry from a larger J195pt-31p value (3668 Hz). The lH and 13C{lH}NMR spectra of the major product were similar to those of truns-[PdXdPhTRAP)]. These species were easily separated by column chromatography (silica gel, CHzClz; Rf 0.94 for trans, 0.20 for cis). The chelated mononuclear structure of the truns-[PtClz(PhTRAP)] (10) was concluded from FAB-mass spectra and from a molecular weight determination by VPO analysis (MW calcd 1060.5, obsd 1120 in CHCld. Reaction of unsymmetrical TRAP l e with PtC12(MeCN)2 at 35 "C for 30 min gave trans-PtClyle (11)as a single isomer. The 31P{1H}NMR spectrum (202 MHz) showed an AB quartet with a 31P-31Pcoupling constant of 490 Hz. Such a large value was in agreement with the trans geometry. (14)Rahn, J. A,; Baltusis, L.; Nelson, J. H. Inorg. Chem. 1990,29, 750 and references cited therein.
G%-JC23 C24
Figure 6. ORTEP drawing (30% probability level) and atom-labeling scheme for t r a n s - [ R h C l ( C O ) { ( S , S ) - ( ~ ~ ) FurTRAP}] (14) (hydrogen atoms are omitted for clarity). Only one of the two molecules in a unit cell is shown. The second molucule is in essence a rotamer in which 0 3 and C31 and 05 and C39 are interchanged.
Iridium Complex. Vaska-type complex truns-[IrCl-
(CO){(S,S)-(R,R)-PhTRAP}l (12) was prepared by the reaction of (S,S)-(R,R)-PhTRAPwith dicarbonylchloro(p-toluidine)iridium(I). Because of the chirality of PhTRAP, resonances of the two phosphorus atoms of 12 appeared with different chemical shifts (21.0 and 40.4 ppm) and coupled with each other with a J p - p value of 344 Hz. Such asymmetry was also observed in both lH and 13C{lH} NMR spectra. From the large 31P-31P coupling constant, the iridium complex was deduced to have trans geometry. Rhodium Complexes. Reaction of (S,S)-(R,R)-PhTFUP with [{Rh(C0)2}2@-C1)21proceeded at room temperature with evolution of carbon monoxide to give trans-[RhCl(CO){(S,S)-(R,R)-PhTRAP}l (13). The 31P{lH} NMR spectrum showed a pair of double doublets due to 31P-31P (J= 355 Hz) and 103Rh-31Pcoupling (J = 129 and 126 Hz). The 'H and l3C{IH} NMR spectra were similar to those of iridium complex 12. X-ray crystal structures have been determined for truns-[RhCl(CO){( S , S ) - ( R , R ) - F u f l ~ } l ( 1 4each ) , unit cell containing a set of independent molecules. An ORTEP drawing with atom-labeling scheme for one of the two molecules is shown in Figure 6.15 Bond distances and angles are given in Table 3. The environment of Rh is almost the same as that of Pd in PhTRAP-Pd complex 7. Bond angles P(l)-Rh(l)-P(2) and Cl(l)-Rh(l)-C(l) are 161.06(4) and 176.2(2)", respectively. Dihedral angles P(l)-C(2)-C(4)-C(8) and P(2)-C(14)-C(16>-C(20) are 100.9(4) and 92.8(5)", respectively. The angle between the least-squares planes through the two linked Cp rings (C4-C8, C16C20) is 124.7". Contrary to PhTRAP coordinating to the Pd atom, FurTRAP adopts essentially C2 symmetrical conformation in coordination to the Rh atom (compare (15) The structure of another molecule is similar to that shown in Figure 6. Crystallographic data were deposited with the Cambridge Crystallographic Data Centre.
Trans-Chelating Chiral Diphosphine Ligands
Organometallics, Vol. 14, No. 10, 1995 4553 procedures. PdC12(MeCN)2 was prepared by boiling a suspension of PdCl2 in MeCN. [{Rh(CO)2}2(u-C1)21was purchased and used without purification.
(R)-2-[(S)-l~(NJV-Dimethylamino)ethyl]-l-iodoferrocene [(S)-(R)-3] was prepared from (SI-2according to the literature procedure.8 The product was obtained as a mixture with the starting material (87% conversion, (S)-(R)-3/(S)-(S)349-2 in a n 85/2/13 molar ratio) and was used without further purification: brown solid; mp 45-48 "C; lH NMR (200 MHz, CDCl3) 6 1.50 (d, J = 6.8 Hz, 3 H), 2.15 (s,6 H), 3.62 (4, J = 6.8 Hz,1H), 4.12 (9, 5 H), 4.15 (dd, J = 2.6 and 1.2 Hz, 1H), 4.24 (t, J = 2.6 Hz, 1 H), 4.46 (dd, J = 2.6 and 1.2 Hz, 1 H); 13C NMR (50 MHz, CDC13) 6 15.94, 41.16 (2 C), 45.44, 57.52, 65.52, 68.13, 71.61 (Cp), 74.25, 90.11; HRMS (EI) calcd for CldHIsFeIN, 382.9830, found (mlz)382.9824.
Figure 7. View of t r a n s - [ R h C l ( C O ) { ( S , S ) - ( R p ) - ~ } ] (14)normal to the virtual square plane (hydrogen atoms are omitted for clarity). Table 3. Selected Bond Lengths (A)and Angles (deg) of 14 Bond Lengths (A) 2.365(2) Rh(l)-P(l) 2.300(1) Rh(1)-C( 1) 1.859(1) P(1)-C(26) 1.799(5) P(2)-C(14) 1.796(5) P(2)-C(38)
Rh(l)-C1(1) Rh(l)-P(2) P(1)-C(2) P(l)-C(30) P(2)-C(34) C1(1)-Rh( 1)-P( 1) Cl(l)-Rh(l)-C(l) P(l)-Rh(l)-C(l) Rh(l)-P(l)-C(2) Rh(l)-P(l)-C(BO) C(2)-P(l)-C(30) Rh(l)-P(2)-C(14) Rh(l)-P(2)-C(38) C(14)-P(2)-C(38)
Angles (deg) 86.78(5) Cl(l)-Rh(l)-P(2) 176.2(2) P(l)-Rh(l)-P(2) 92.6(2) P(2)-Rh(l)-C(l) 105.5(1) Rh(l)-P(l)-C(26) 118.0(2) C(2)-P(l)-C(26) 108.7(2) C(26)-P(l)-C(30) 109.7(1) Rh(l)-P(2)-C(34) 114.7(2) C(14)-P(2)-C(34) 101.4(2) C(34)-P(2)-C(38)
2.301(1) 1.807(1) 1.806(5) 1.864(4) 1.815(5) 93.81(5) 161.06(4) 88.0(2) 118.9(2) 103.4(2) 101.1(2) 121.5(2) 104.3(2) 102.9(2)
Figure 7 with Figure 5). The difference in conformation between PhTRAP-Pd complex 7 and Fur"-Rh complex 14 m a y be attributed to the difference in steric bulkiness of the aryl substituents on the phosphorus atoms.
Experimental Section General Procedures. Optical rotations were measured with a Perkin-Elmer 243 polarimeter. NMR spectra were obtained with JEOL JNM-A500 (lH, 500.16 MHz; 13C, 125.77 MHz; 31P, 202.46 MHz), JEOL JNM-A400 (lH, 399.78 MHz; 13C,100.53 MHz; 31P,161.83 MHz), and Varian VXR-200 (lH, 200.06 MHz; W , 50.31 MHz; 31P,80.98 MHz) spectrometers. Most of the lH and 13C NMR spectra of new compounds described below were measured at two different frequencies to determine coupling constants with 31P. lH NMR spectra were recorded in 6 ppm relative to internal Me4Si (6 0). 13C{'H} NMR spectra were recorded in 6 ppm relative to CDC13 (6 77.0). 31P{1H}NMR spectra were recorded in 6 ppm relative to external 85% aqueous H3P04 (6 0). IR spectra were recorded with a Hitachi 270-30 spectrophotometer. High-resolution mass spectra (HRMS) were obtained with JEOL JMS-DX3OO and JEOL JMS-SXlO2A spectrometers. Preparative highperformance liquid chromatography (HPLC) was performed with a YMC SHO43-5 (silica gel, 20 mm x 250 mm) column. Materials. (R)-and (S)-2,7diarylphosphine oxides (Ar2P(0)H: Ar = Ph, 4-MeOC&,4-C1C& 4-MeC6H4),l6and [IrCl(CO)z(p-t~luidine)]~~ were prepared according to the literature (16)(a) Hunt, B. B.; Saunders, B. C. J. Chem. Soc. 1957,2413.(b) Grayson, M.;Farley, C. E.; Streuli, C. A. Tetrahedron 1967,23,1065. (17)Klaubunde, U.Inorg. Synth. 1974,15, 82.
(R)-2-[(S)-l-(Diphenylphosphinyl)ethyll-l-iodoferrocene [(S)-(R)-4al: In a nitrogen atmosphere, was added dropwise 1.6 M n-butyllithiumhexane (13.0 mL) to an icecooled solution of diphenylphosphine oxide (4.05 g, 20.0 mmol) in dry THF (50 mL) over 2 min. The brown solution was stirred at room temperature for 1.5 h. The solvent was evaporated, and the remaining lithium diphenylphosphinite was dried in vacuo. (S)-(R)-3in another reaction flask was dissolved in CHzClz (10 mL), and iodomethane (8.0 g, 56 mmol) was added with ice cooling. The mixture was stirred at room temperature for 30 min. The solvent was evaporated, and the remaining ammonium salt was dried in vacuo. The ammonium salt was dissolved in dry MeCN (110 mL), and the solution was transferred t o the phosphinite salt at room temperature. The mixture was refluxed for 1h and was cooled to room temperature. After dilution with 100 mL of water, the mixture was extracted twice with ether. The organic layer was washed twice with saturated NaCl and dried over MgS04. The residue was passed through a column of alumina (EtOAddiethylamine = 15/1) to give a mixture of 4 a and 5a, which was formed mainly by the reaction of 2 (5.37 g, 4 d 5 a = 4.5/1, quantitative yield, the yield from 3 to 4a was 96%). This crude product was used without further purification: viscous oil; -17.9 (for pure 4a, c 0.504, CHC13); lH NMR (400 MHz, CDC13) 6 1.68 (dd, J p - H = 15.4 and JH-H= 7.3 Hz, 3 H), 3.29 (dq, J p - H = 6.5 and JH-H = 7.3 Hz, 1 H), 4.16 (s, 5 H), 4.28 (dd, JH-H = 2.5 and 1.4 Hz, 1 H), 4.31 (dt, J p - H * 0.5 and JH-H= 2.5 Hz, 1H), 4.55 (ddd, J p - H = 1.3, JH-H= 2.5 and 1.4 Hz, 1H), 7.147.25 (m, 4 H), 7.31-7.36 (m, 1 H), 7.54-7.63 (m, 3 H), 7.907.97 (m, 2 H); 13CNMR (100 MHz, CDC13) 6 16.13 (d, Vp-c = 1.8 Hz), 34.29 (d, 'Jp-c = 65.9 Hz), 47.04 (d, 3Jp-c = 2.4 Hz), 66.61 (d, 3 J p - ~or 4 J p - ~= 1.9 Hz), 68.90, 71.34 (Cp), 73.23, 89.21, 127.69 (d, Vp-c = 11.6 Hz, meta), 128.66 (d, Vp-c = 11.0 Hz, meta), 130.82 (d, ~JP-c = 92.8 Hz, ipso), 131.40 (d, 4 J p - ~= 3.0 Hz, para), 131.59 (d, lJp-c = 98.3 Hz, ipso), 131.64 (d, 'Jp-c = 8.6 Hz, ortho), 131.81 (d, Vp-c = 9.2 Hz, ortho), 131.84 (d, 4 J p - ~= 3.1 Hz, para); 31PNMR (81MHz, CDC13) 6 34.40; HRMS (EI) calcd for C24HzzFeIOP, 539.9800, found (m/ 2 ) 539.9793. (R)-2-[(S)-l-{ Bis(4-methoxyphenyl)phosphinyl}ethyll1-iodoferrocene [(S)-(R)-4blwas prepared from (S)-(R)-3 and bis(4-methoxypheny1)phosphine oxide as a mixture with Sb as described for the preparation of 4a and was used without further purification (total 91%, the yield from 3 t o 4b was 72%): viscous oil; 'H NMR (200 MHz, CDC13) 6 1.65 (dd, JP-H = 15.2 and JH-H = 7.2 Hz, 3 H), 3.19 (dq, JP-H = 6.6 and JH-H = 7.2 Hz, 1H), 3.74 (s, 3 H), 3.89 (s, 3 H), 4.15 (s, 5 H), 4.31 ( L U Xsystem, d, 2 HI, 4.51 (AAX system, t, ~'JH-H + 'JH-H~ = 4.2 Hz, 1 H), 6.68 (pseudo-dd, 2 H), 6.9-7.2 (m, 4 H), 7.83 (pseudo-dd, 2 H); 13CNMR (50 MHz, CDC13) 6 16.05 (d, %JP-c = 2.0 Hz), 34.67 (d, 'Jp-c = 67.1 Hz), 47.29 (d, 3Jp-c = 2.8 = -2.3 ~Hz), 68.80, Hz), 55.17, 55.32, 66.51 (d, 3 J ~or-4~J ~ 71.31 (Cp), 73.16, 89.34 (d, 'Jp-c = 1.2 Hz), 113.19 (d, 3 J ~ - c= 12.6 Hz, meta), 114.15 (d, 3 J p - ~= 12.1 Hz, meta), 121.95 (d, lJp-c = 99.1 Hz, ipso), 123.32 (d, lJp-c = 104.8 Hz,ipso), 133.34 (d, 'Jp-c = 9.6 Hz, ortho), 133.61 (d, 'Jp-c = 10.6 Hz,
4554 Organometallics, Vol. 14, No. 10,1995
Sawamura et al.
ortho), 161.98 (d, 4 J p - ~= 2.8 Hz, para), 162.28 (d, 4 J p - ~= 3.0 ratio) was added activated copper powderlo (25 g), and the Hz, para); 31PNMR (81 MHz, CDCls) 6 34.30; HRMS (EI) calcd solvent was evaporated. The remaining mixture was heated under an argon atmosphere at 130 "C for 12 h and was cooled for C26H&eI03P, 600.0014, found ( d z ) 599.9988. (R)-2-[~S)-1-{Bis(4-chlorophenyl)phosphinyl}ethyll-l-to room temperature. Organic materials were extracted with CH2C12. The solvent was evaporated, and the residue was iodoferrocene [(S)-(R)-4c]was prepared from (S)-(R)-3and chromatographed on silica gel (benzene/EtOAc = 2/11. Fracbis(4-chloropheny1)phosphine oxide as a mixture with Sc as tions containing 6a were collected and concentrated. Recrysdescribed for the preparation of 4a and was used without tallization from toluene gave 2.11 g (64%) of (S,S)further purification (total 93%, the yield from 3 to 4c was (R,R)-6a.(toluene)l,5: orange crystals; mp 245-250 "C (de82%): orange amorphous solid; mp 63-65 "C; IH NMR (200 camp); [ a I z 6+130 ~ (c 1.02, CHC13); 'H NMR (400 MHz, CDCl3) = 15.7 and JH-H = 7.3 Hz, 3 H), MHz, CDC13) 6 1.67 (dd, JP-H 6 1.65 (dd, J p - H = 16.8 and JH-H = 7.4 Hz, 6 HI, 3.81 (dq, 3.24 (dq, JP-H = 6.5 and JH-H = 7.3 Hz, 1 H), 4.17 (s, 5 H), J p - H = 11.0 and JH-H = 7.4 Hz, 2 HI, 4.01 (m, 2 H), 4.08 (t, 4.32 (AAX system, d, 2 H), 4.50 (AAX system, t, ['JH-H JH-H = 2.6 Hz, 2 H), 4.35 (s, 10 H), 4.35 (m, 2 H), 6.99-7.06 2 J ~= - 4.2 ~ lHz, 1H), 7.0-7.2 (m, 4 H), 7.5-7.6 (m, 2 H), 7.8(m, 4 H), 7.28-7.33 (m, 2 H), 7.40-7.52 (m, 6 H), 7.60-7.68 7.9 (m, 2 HI; NMR (100 MHz, CDC13) 6 15.92 (d, 2 J p - ~= (m, 4 H), 7.77-7.84 (m, 4 H); 13C NMR (100 MHz, CDCl3) 6 2.2 Hz), 34.38 (d, 'Jp-c = 66.9 Hz), 46.88 (d, Vp-c = 3.0 Hz), 19.14,30.23 (d, IJP-C= 69.0 Hz), 65.39,68.32 (d, VP-Cor 4 J ~ - ~ or -4~ J ~=-2.1 ~ Hz), 69.07, 71.44 (Cp), 73.39, 66.49 (d, 3 J ~ = 5.5 Hz), 69.36 (Cp), 72.56,84.48 (d, 2 J ~or- 3~ J ~=-6.8 ~ Hz), 88.54 (d, 2 J p - ~= 1.2 Hz), 128.09 (d, Vp-c = 12.2 Hz, meta), 90.58, 128.07 (d, VP-C= 11.0 Hz, metal, 128.18 (d, 3 J ~ =- ~ 128.92 (d, IJP-c= 93.7 Hz, ipso), 129.17 (d, V p - c = 11.7 Hz, 11.6 Hz, meta), 130.95 (d, 4 J ~=- 2.4 ~ Hz, para), 131.22 (d, metal, 129.73 (d, IJP-c= 99.9 Hz, ipso), 132.91 (d, 2 J p - ~= 9.3 Hz, ortho), 133.08 (d, 2 J p - ~= 10.2 Hz, ortho), 138.19 (d, 4 J ~ - ~ 4 J p - ~= 3.0 Hz, para), 131.36 (d, 2 J p - ~= 9.1 Hz, ortho), 132.03 (d, IJp-c = 94.0 Hz, ipso), 132.25 (d, 2 J p - ~= 8.5 Hz, ortho), = 3.4 Hz, para), 138.74 (d, 4 J p - ~= 3.4 Hz, para); 31PNMR (81 133.85 MHz, CDC13) B 32.87; HRMS (EI) calcd for C Z ~ H ~ O C ~ ~ F ~ I O P , (d, I J p - c = 94.6 Hz, ipso); 31PNMR (81MHz, CDC13) 6 35.59. Anal. Calcd for C ~ ~ . J I & ~ ~ OC, Z P72.83; ~ : H, 5.85. 607.9023, found (mlz)607.8995. (R)-2-[(S)-1-(Di-2-furylphosphinyl)ethyl]-l-iodofer-Found: C, 72.95; H, 5.79. (R,R)-2,2"-Bis[(S)-l-[bis(4methoxyphenyl)phosphinyl]rocene [(S)-(R)-4dl.To a solution of furan (10.36 g, 152 ethyl]-1,l"-biferrocene[(S,S)-(R,R)-Gblwas prepared as mmol) in 90 mL of ether was added dropwise 1.57 M n-BuLil described for the preparation of 6a and was purified by flash hexane (65 mL, 102 mmol) at 0 "C over 1 h, and the mixture chromatography (silica gel, benzenefEtOAc): 32% yield; orange was refluxed for 2 h. A solution of diethyl phosphite (4.22 g, (c 1.00, CHC13); amorphous solid; mp 170-174 "C; [ a I z S+65.8 ~ 31 mmol) in 20 mL of ether was added dropwise to the mixture IH NMR (500 MHz, CDC13) 6 1.63 (dd, JP-H = 16.6 and JH-H at 0 "C over 30 min. The mixture was stirred at room = 7.3 Hz, 6H), 3.70 (s, 6 H), 3.72 (m, 2 H, a-CHI, 3.84(s, 6 H), temperature for 1h and was then evaporated in vacuo. The 4.08 (m, 4 H), 4.28 (m, 2 HI, 4.34 (s, 10 HI, 6.56 (pseudo-dd, 4 reaction of the residual solid [lithium bis(2-fury1)phosphinitel HI, 6.95 (pseudo-dd, 4 HI, 7.52 (pseudo-dd, 4 HI, 7.69 (pseudowith the ammonium salt prepared from 6.90 g (14.4 mmol) of dd, 4 H); NMR (125 MHz, CDC13) 6 19.33 (d, 2Jp-c = 0.5 (80 mol % purity) gave a mixture of (S)-(R)-4d crude (S)-(R)-3 Hz), 30.35 (d, 9 p - c = 68.7 Hz), 55.06, 55.20, 65.37, 68.23 (d, and 5d (6.86 g, 4d/5d = 1011 in a molar ratio, yield from 3 to 3 J p - ~or 4 J p - ~= 5.4 Hz), 69.27 (Cp), 72.20, 84.47 (d, 2 J p - ~or 4d was 95%,which was used without further purification: lH Vp-c = 6.1 Hz), 90.72, 113.61 (d, Vp-c = 12.2 Hz, metal, NMR (400 MHz, CDC13) 6 1.71 (dd, JP-H = 17.1 and JH-H = 113.69 (d, Vp-c = 12.2 Hz, metal, 123.30 (d, IJp-c = 100.6 7.3 Hz, 3 HI, 3.34 (dq, JP-H = 11.1and JH-H = 7.4 Hz, 1 H), Hz, ipso), 125.35 (d, 'JP-C= 100.7 Hz, ipso), 133.16 (d, 2 J p - ~ 4.14 (s, 5 H), 4.20 (m, 1 H), 4.24 (t,J = 2.5 Hz, 1H), 4.36 (m, = 10.7 Hz, ortho), 133.92 (d, 2 J ~ - = c 9.9 Hz, ortho), 161.56 (d, 1HI, 6.35 (m, 1H), 6.51 (m, 1H), 6.70 (m, 1H), 7.18 (m, 1H), 4 J p - ~= 2.3 Hz, para), 161.88 (d, 4 J p - ~= 2.3 Hz, para); 31P 7.54 (m, 1 H), 7.71 (m, 1 H); 13C NMR (100 MHz, CDC13) 6 NMR (81 MHz, CDC13) 6 35.64; HRMS (FAB)calcd for C52H5215.51,35.62 (d, Jc-p = 75.7 Hz), 45.46 (d, J c - p = 3.0 Hz), 66.20 FezOsPz, 946.1938, found (mlz)946.2012. (d, J c - p = 2.5 Hz), 68.82, 71.43, 73.72, 88.12, 110.08 (d, Jc-p = 8.0 Hz), 110.73 (d, Jc-p = 8.5 Hz), 122.63 (d, Jc-p = 18.3 (R,R)-2,2"-Sis[(S)-l-{ bis(4-chloropheny1)phosphinyl)Hz), 123.36 (d, J c - p = 17.7 Hz), 145.87 (d, Jc-p = 133.7 Hz), ethyl]-1,l"-biferrocene[(S,S)-(R,R)-Gc]was prepared as 146.06 (d, Jc-p = 138.0 Hz), 147.68 (d, Jc-p = 7.3 Hz), 148.02 described for the preparation of 6a,except that the coupling (d, Jc-p = 7.3 Hz); 31PNMR (81 MHz, CDC13) 6 14.68; HRMS was performed at 170 "C for 8 h and purified by column (E11calcd for C ~ O H I B F ~ I 519.9410, O~P, found (mlz)519.9408. chromatography (silica gel, benzenefEtOAc): 37% yield; orange (R)-24(S)-l-{ Bis(4-methylphenyl)phosphinyl)ethyl]-l(c 1.04, CHC13); amorphous solid; mp 137-139 "C; [ a I z 5+189 ~ iodoferrocene [(S)-(R)-4e] was prepared from (S)-(R)-3 and * 'H NMR (500 MHz, CDC4) 6 1.59 (dd, JP-H = 17.4 and JH-H bis(4-methy1phenyl)phosphineoxide as a mixture with 5e as = 7.3 Hz, 6 H), 3.69 (dq, JP-H = 11.9 and JH-H = 7.3 Hz, 2 H), described for the preparation of 4a and was used without 3.89 (br s, 2 H), 4.13 (t, JH-H = 2.5 Hz, 2 HI, 4.35 (s, 10 H), further purification (quantitatively, the yield from 3 to 4e was 4.46 (br s, 2 H), 6.94 (pseudo-d, 4 H), 7.41 (pseudo-dd, 4 H), 88%): orange crystals; mp 180-185 "C (decomp);IH NMR (200 7.60 (pseudo-dd, 4 HI, 7.69 (pseudo-dd, 4 HI; NMR (125 = 15.3 and JH-H = 7.3 Hz, 3 H), MHz, CDC13) 6 1.66 (dd, JP-H MHz, CDC13) 6 19.04, 29.79 (d, 'Jp-c = 70.7 Hz), 65.56, 67.95 2.27 (s, 3 H), 2.45 (s, 3 H), 3.23 (dq, JP-H = 6.7 and JH-H = 7.3 (d, 3 J p - ~or 4Jp-c = 4.3 Hz), 69.43, 72.93, 84.34 (d, V - Cor Hz, 1 H), 4.15 (s, 5 H), 4.30 (AAX system, d, 2 H), 4.52 (AAX 3 J p - ~= 7.5 Hz), 90.35, 128.48 (d, 3 J p - ~= 11.8 Hz, meta), system, t, I'JH-H + 2 J ~ =- ~3.8i Hz, 1 H), 6.9-7.2 (m, 4 H), ~ Hz, meta), 130.17 (d, 'JP-c= 96.4 Hz, 128.63 (d, 3 J ~=- 11.8 7.3-7.4 (m, 2 HI, 7.7-7.8 (m, 2 HI; 13CNMR (50 MHz, CDC13) ipso), 131.84 (d, IJp-c = 95.3 Hz, ipso), 132.70 (d, 2 J p - ~= 9.7 6 16.19 (d, 2Jp-c = 2.0 Hz), 21.49 (d, 'Jp-c = 1.3 Hz), 21.62 (d, Hz, ortho), 133.65 (d, 'Jp-c = 9.6 Hz, ortho), 137.92 (d, 4Jp-c 'JP-c = 1.3 Hz), 34.35 (d, 'JP-c = 66.3 Hz), 47.18 (d, 3Jp-c = = 3.3 Hz, para), 138.09 (d, 4 J p - ~= 3.2 Hz, para); 31PNMR (81 2.9 Hz), 66.57 (d, 3 J ~or- 4~ J ~=-2.3 ~ Hz), 68.79, 71.31 (Cp), MHz, CDC13) 6 34.77. Anal. Calcd for C48H40C14Fe202P2: C, 73.12, 89.37 (d, 2 J ~ - = c 1.1Hz), 127.64 (d, 'Jp-c = 95.2 Hz, 59.79; H, 4.18. Found: C, 59.94; H, 4.30. ipso), 128.37 (d, 3 J p - ~ = 12.0 Hz, meta), 128.48 (d, lJp-c = (R,R)-2,2"-Bis[~S)-l-(di-2-furylphosphinyl)ethyl]-l,l"100.7 Hz, ipso), 129.33 (d, 3 J p - ~= 11.5 Hz, metal, 131.57 (d, biferrocene [(S,S)-(R,R)-Gd]was prepared as described for 2 J ~ - c= 8.9 Hz, ortho), 131.75 (d, 'Jp-c = 9.9 Hz, ortho), 141.59 the preparation of 6a and was purified by a column chroma= 2.9 Hz, para), 142.09 (d, 4 J p - ~= 2.8 Hz, para); 3lP (d, 4J~-c tography on alumina (EtOAc/EtzNH = 15/11 followed by a NMR (81 MHz, CDC13) 6 34.59; HRMS (EI)calcd for recrystallization from CHzClz/hexane: 65% yield; orange FeIOP, 568.0115, found (mlz)568.0104. crystals; mp 140-145 "C; [aIz5~ -408 (c 0.2, CHC13); IH NMR (R~)-2,2"-Bis~~S~-l-(diphenylphosphinyl)ethyl~-l,l"(200 MHz, CDC13) 6 1.79 (dd, JP-H = 18.6 Hz, JH-H = 7.4 Hz, biferrocene [(S,S)-(R,R)-GaI. To a CHzClz (25 mL) solution 6 H), 3.9-4.1 (m, 2 H), 4.15 (m, 2 HI, 4.28 (m, 2 H), 4.35 (m, (4.32 g, 6.84 mmol for 4a,4d5a = 82/18 in molar of (S)-(R)-4a 12 H), 6.36 (m, 2 HI, 6.57 (m, 2 HI, 6.68 (m, 2 H), 7.20 (m, 2
+
Organometallics, Vol. 14, No. 10, 1995 4555
Trans-Chelating Chiral Diphosphine Ligands
C-2"), 127.19 (Ph-1-para), 127.46 (t, I3Jp-c + 4 J ~ =~ 6.7 I Hz, Ph-2-meta), 128.00 (t, I3Jp-c 4J~-cI= 4.8 Hz, Ph-1-meta), 128.33 (Ph-2-para), 132.14 (quint, I2Jp-c + 3 J ~ -=~18.3 I Hz, = 21.4 Hz, Ph-2Ph-1-ortho), 135.11 (quint, I2Jp-c 3J~-~I ortho), 136.13 (split into six lines, 1lJp-c + %TP-cI = 21.3 Hz, Ph-2-ipso), 139.01 (split into six lines, 1'Jp-c 'JP-cI = 18.9 Hz, Ph-1-ipso); 31PNMR (81 MHz, CDC13) 6 2.19; full assignment of the spectra has been done with the aid of 'H{ 'H} NOE (Table 1, Figure l),HETCOR, HMBC, and 13CINADEQUATE (see supporting information for the 2D NMR experiments). (4-methylphenyl)phosphinyl}ethyl]-l,l"-biferrocene Anal. Calcd for C48H44FezPz: C, 72.56; H, 5.58. Found: C, 72.68; H, 5.40. [(S,S)-(R,R)-6e] was prepared from (S)-(R)-4a(1.02 g, conAlthough product la can be recrystallized from CHZCld taining 1.61 mmol of 4a) and (S)-(R)-4e(1.02 g, containing EtOH, benzene/EtOH, etc. to give solvent-containing orange 1.91 mmol of 4e)as described for the preparation of 6a. The crystals, the amounts of crystallization solvent were nonspecrude product was purified by FTLC (silica gel, hexane/EtOAc cific. = 1/3) followed by HPLC (hexane/l,2-dichloroethane/ethanol NOE Experiment on la. The IH{'H} NOE experiment = 24/8/1) to give 0.156 g of 6e (23%): orange amorphous solid; was performed at 200 MHz with 20 mg of (S,S)-(R$)-lain mp 166-170 "C; [ a I z 5+116 ~ (c 1.01, CHCl3); IH NMR (500 CDC13 (0.6 mL) at room temperature. The decoupler was set MHz, CDC13) 6 1.61 (dd, J p - H = 16.8 and JH-H= 7.3 Hz, 3 H), to the resonance of a-methyl proton and was turned on for 16 1.66 (dd, J p - H = 16.8 and JH-H = 7.3 Hz, 3 H), 2.27 (s, 3 H, s. The power of irradiation was set so that the intensity of tol-l-CHg), 2.39 (s, 3 H, tol-2-CHs), 3.68 (dq, J p - H = 11.6 and the signal saturated might become around 70% of the original JH-H= 7.3 Hz, 1H), 3.87 (dq, J p - H = 10.5 and JH-H= 7.3 Hz, intensity. This preirradiation period was followed by a short 1H), 3.99 (m, 1H), 4.07 (t,JH-H= 2.6 Hz, 1H), 4.08 (t,JH-H (0.05 s) switching time to prevent the occurrence of unwanted = 2.6 Hz, 1H), 4.10 (m, 1 H), 4.31 (m, 2 H), 4.33 (s, 5 H), 4.35 decoupling immediately followed by a 90"-acquisitionpulse and (5, 5 H), 6.86 (pseudo-dd, 2 H, tol-1-meta), 6.97 (pseudo-td, 2 a 4-s acquisition. Eight transients were acquired with the H, Ph-1-metal, 7.24 (pseudo-dd, 2 H, tol-2-meta), 7.27 (pseudodecoupler on resonance. Next, for each a-H, H-3, H-4, and td, 1 H, Ph-1-para), 7.42 (pseudo-td, 2 H, Ph-2-meta), 7.46 H-5, eight transients were acquired by the same procedure. (pseudo-td, 1H, Ph-2-para), 7.47 (pseudo-dd, 2 H, tol-1-ortho), Reference spectra were obtained in a similar manner with the 7.65 (pseudo-dd,4 H, Ph-1-ortho and tol-2-ortho), 7.83 (pseudodecoupler frequency set to an empty region of the spectrum, ddd, 2 H, Ph-2-ortho); the coupling network was deduced by and eight reference transients were acquired. A series of the an lH-lH COSY experiment; 13C NMR (125 MHz, CDC13) 6 above procedures was repeated eight times; a total of 384 19.20(d,2Jp-~~1.1H~),19.23,21.44(d,5Jp-~~1.3H~),21.56 transients were collected. Percent NOE enhancements were (d, 'Jp-c = 1.3 Hz), 30.06 (d, 'Jp-c = 68.6 Hz), 30.39 (d, 'Jp-c determined by integration of the difference spectra as totals = 69.4 Hz), 65.35, 65.42, 68.05 (d, 3 J ~ or -4~J ~ = -4.6~Hz), of the enhancements for all equivalent protons. 68.56 (d, 3 J p - ~or 4 J p - ~= 5.3 Hz), 69.30 (Cp), 69.34 (Cp), 72.35, (R,R)-2,2"-Bis[(S)-l-{bis(4-methoxyphenyl)phosphino}72.49, 84.31 (d, Vp-c or 3 J p - ~= 6.9 Hz), 84.63 (d, Vp-c or 3J~ = 5.4 - ~Hz), 90.66 ( 2 0 , 128.07 (d, 3 J ~ =11.5 ~ Hz, metal, ethyl]-1,l"-biferrocene[(S,S)-(R,R)-AnisTRAP (lb)]was prepared as described for the preparation of la: 85% yield; 128.08 (d, 3 J p - ~= 10.7 Hz, metal, 128.36 (d, lJp-c = 96.7 Hz, orange amorphous solid; mp 104-108 "C; [ a l z 5+321 ~ (c 0.53, ipso), 128.79 (d, 3 J p - ~= 12.2 Hz, metal, 128.94 (d, 3 J p - ~= 11.5 Hz, metal, 130.65 (d, IJp-c = 96.9 Hz, ipso), 130.77 (d, CHCl3);lH NMR (500 MHz, CDC13) 6 1.36 (pseudo-t, 6 H), 3.36 4 J p - ~= 2.3 Hz, para), 131.13 (d, 4 J p - ~= 2.3 Hz, para), 131.35 (q, JH-H= 7.2 Hz, 2 H), 3.67 ( s , 6 HI, 3.75 (dd, JH-H= 2.4 and 1.4 Hz, 2 H), 3.77 (s, 6 H), 4.07 (t,JH-H= 2.4 Hz, 2 H), 4.30 (s, (d, 'Jp-c = 9.1 Hz, ortho), 131.42 (d, 'Jp-c = 9.2 Hz, ortho), 10 H), 4.52 (dd, JH-H= 2.4 and 1.4 Hz, 2 H), 6.60 (pseudo-d, 132.09 (d, 'Jp-c = 8.4 Hz, ortho), 132.37 (d, 'Jp-c = 94.6 Hz, ipso), 132.39 (d, 'Jp-c = 9.1 Hz, ortho), 133.92 (d, 'Jp-c = 93.8 4 H), 6.76 (pseudo-d, 4 H), 7.18-7.28 (m, 8 H); 13CNMR (125 =~ 5.0 I Hz), 29.10 (split Hz, ipso), 141.15 (d, 4 J p - ~= 3.0 Hz, para), 141.52 (d, 4 J p - ~= MHz, CDC13) 6 18.01 (t, I2Jp-c + 3 J ~ 2.3 Hz, para); 31PNMR (81 MHz, CDC13) 6 35.77,35.83; HRMS into six lines, 1lJp-c 'Jp-cI = 14.1 Hz), 54.99, 55.08, 65.07, (FAB)calcd for C50H&e202P2,854.1828, found ( m l z )854.1875. 68.28 (t, I3Jp-c 4Jp-cI = 9.4 Hz), 69.16 (($1, 72.24 (t, I4Jp-c 'Jp-cI = 2.3 Hz), 84.19 (t, I3Jp-c + 4Jp-c/ = 4.0 Hz), 93.63 (R,R)-2,2"-Bis[(SI-1-(dipheny1phosphino)ethyll -l,l"-bi(split into six lines, I2Jp-c 3Jp-cI = 18.6 Hz), 113.33 (t, I3Jp-c ferrocene [(S,S)-(R,R)-PhTRAP (la)]. In a glass tube was 4J~= -~ 7.9 I Hz, metal, 113.74 (t, I3Jp-c + 4 J ~ - ~ I = 5.5 Hz, placed 918 mg (0.952 mmol) of (S,S)-(RF)-4a.(toluene)l,5. After meta), 127.42 (split into six lines, 1lJp-c + 'Jp-cI = 17.7 Hz, benzene (2.5 mL), Et3N (1.1mL, 7.9 mmol), and HSiCl3 (0.6 ipso), 130.13 (split into six lines, 1IJp-c + 'Jp-cI = 14.4 Hz, mL, 5.9 mmol) were successively added, the tube was cooled ipso), 133.38 (quint, 1Vp-c + 3 J ~ =~ 20.2 I Hz, ortho), 136.65 with dry ice-acetone, sealed in vacuo, and heated at 100 "C -~ 22.8 I Hz, ortho), 158.93 (para), 160.20 (quint, 1'Vp-c 3 J ~ = for 10 h. The reaction mixture was cooled to room tempera(para); 31P NMR (81 MHz, CDC13) 6 0.30. Anal. Calcd for ture, 30% aqueous NaOH was carefully added to the mixture, C ~ ~ H ~ Z F ~C, Z 68.29; O ~ P H, ~ : 5.73. Found: C, 68.06; H, 5.69. and the whole was warmed at 60 "C for 5 min to dissolve (R,R)-2,2"-Bis[(S)-l-{ bis(4-chlorophenyl)phosphino}silicon-containing precipitate. After the mixture had cooled ethyl]-1,l"-biferrocene[(S,S)-(R,R)-Cl-PhW (lc)] was to room temperature, the organic layer was separated, washed prepared as described for the preparation of la: 87% yield; once with water, once with brine, and dried over MgS04. orange amorphous solid; mp 115-119 "C; [ a I z 5$459 ~ (c 0.43, Purification by column chromatography (alumina, benzene) CHC13);lH NMR (400 MHz, CDC13) 6 1.30 (split into six lines, gave 741 mg (98%) of la: orange amorphous solid; mp 986 H), 3.35 (9, JH-H= 7.0 Hz, 2 H), 3.87 (dd, JH-H= 2.5 and 103 "C; [ a I z 5+426 ~ (C 0.51, CHCl3); 'H NMR (400 MHz, CDCl3) 1.4 Hz,2 H), 4.23 (t,JH-H = 2.5 Hz, 2 H), 4.28 (s,10 H), 4.55 6 1.35 (pseudo-t, 6 H, CH3), 3.49 (9,JH-H= 6.9 Hz, 2 H, a-CHI, (dd, JH-H = 2.5 and 1.4 Hz, 2 H), 7.00-7.07 (m, 8 H), 7.113.79 (dd, JH-H = 2.5 and 1.4 Hz, 2 H, H-3 and H-3'7, 4.12 (t, 7.19 (m, 8 H); 13CNMR (100 MHz, CDC13) 6 15.49, 30.22 (dd, JH-H = 2.5 Hz, 2 H, H-4 and H-4"), 4.29 (8, 10 H, Cp), 4.55 I1Jp-c 'Jp-cI = 21.0 Hz), 65.75, 67.58 (t, I3Jp-c + 4 J ~ = -~l (dd, JH-H= 2.5 and 1.4 Hz, 2 H, H-5 and H-5'7, 7.05-7.40 (m, 5.1 Hz), 69.55 (Cp), 71.14, 84.46 (t, I3Jp-c + 4J~-cI = 5.1 Hz), 20 H, phenyl); I3C NMR (100 MHz, CDC13) 6 17.03 (t, 1'Jp-c + 3 J ~=-2.2 ~ Hz, / CH3),29.25 (split into six lines, 1lJp-c + 2 J ~ - ~ I 92.11 (t, 1'Jp-c + 3Jp-cI = 20.4 Hz), 127.60 (t, I3Jp-c + 4 J ~ - ~ I = 6.4 Hz, metal, 128.43 (t, I3Jp-c + 4 J p - ~ I = 5.1 Hz, metal, = 17.1 Hz, a-CHI, 65.36 (C-4 and C-4"), 68.05 (t, I3Jp-c + 4J~-cI = 6.8 Hz, C-3 and C-3"),69.32 (Cp), 71.67 (t, I4Jp-c + 5 J ~ = - ~ I 133.63 (t, I2Jp-c + 3 J p - ~ I = 19.7 Hz, ortho), 133.89 (para), 134.06 (dd, 1IJp-c 'Jp-cI = 24.1 Hz, ipso), 134.32 (para), 2.3 Hz, C-5 and C-5'7, 84.37 (t, I3Jp-c + 4 J ~ -=~4.2 I Hz, C-1 135.42 (t, I'Jp-c + 3Jp-cI = 12.2 Hz, Ortho), 136.89 (dd, I'JP-c ~ / Hz, C-2 and and C-1'9, 93.08 (quint, I2Jp-c + 3 J ~=- 20.2
H), 7.57 (m, 2 H), 7.77 (m, 2 H); 13CNMR (50 MHz, CDC13) 6 18.70, 32.34 (d, Jc-p = 76.9 Hz), 66.41, 67.33 (d, Jc-p = 5.0 Hz), 69.32, 71.28, 84.25, (d, Jc-p = 4.8 Hz), 87.70, 110.83 (d, Jc-p = 8.3 Hz), 111.15 (d, Jc-p = 8.5 Hz), 122.23 (d, Jc-p = 18.3 Hz), 124.27 (d, Jc-p = 17.2 Hz), 145.98 (d, Jc-p = 133.6 Hz), 147.38 (d, Jc-p = 8.0 Hz), 147.67 (d, Jc-p = 134.3 Hz), 147.87 (d, J c - p = 7.0 Hz); 31P(81 MHz, CDC13) 6 15.6. Anal. Calcd for C ~ O H ~ ~ ~ ~ P Z F ~ ZC,- 56.52; CHZC H,~4.40. Z : Found: C, 56.80; H, 4.46. ~,R)-2-[(S)-1-(Diphenylphosphinyl)ethyl]-2"-[(S)-1-{ bis-
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Sawamura et al.
4556 Organometallics, Vol. 14, No. 10,1995
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2 J p - ~ I= 19.9 Hz, ipso); 31PNMR (81 MHz, CDC13) 6 -0.82. Anal. Calcd for C4sH40C14Fe2Pz: C, 61.84; H, 4.32. Found: C, 62.08; H, 4.58. (R,R)-2,2"-Bis[ (SIl-(di-2-furylphosphino)ethyll1,l"-biferrocene [(S,S)-(R,R)-FurTRAP (Id)] was prepared as described for the preparation of la: 88% yield; orange amorphous solid; mp 115-127 "C; [ a ] 2 5$444 ~ (c 0.28, CHCl3); = 7.2 Hz, JP-H = 'H NMR (400 MHz, CDCl3) 6 1.56 (dt, JH-H 6.5 Hz, 6 HI, 3.27 (9, JH-H = 7.2 Hz, 2 HI, 3.84 (dd, JH-H = 2.7 and 1.4 Hz, 2 H), 4.15 (t, JH-H= 2.7 Hz, 2 H), 4.25 (s, 10 H), 4.46 (dd, JH-H= 2.7 and 1.4 Hz, 2 H), 6.33 (m, 4 H), 6.53 (dd, JH-H = 3.2 and 0.8 Hz, 2 H), 6.68 (ddd, JH-H = 3.2 and 0.8 Hz, Jp-H = 1.9 Hz, 2 H), 7.60 (dd, JH-H= 1.8 and 0.8 Hz, 2 H), 7.66 (dd, JH-H= 1.8 and 0.8 Hz, 2 H); 13C NMR (100 MHz, CDC13) 6 19.23, 31.77 (t, J = 12.9 Hz), 65.79, 66.66 (t,J = 5.9 Hz), 69.38, 70.69 (t, J = 4.7 Hz), 83.98 (t,J = 3.9 Hz), 92.15 (t, J = 20.2 Hz), 110.34 (t, 7.7 Hz), 110.35 (t, J = 4.7 Hz), 119.31 (t, J = 20.4 Hz), 123.22 (t, J = 32.5 Hz), 146.07 (t, J = 2.4 Hz), 146.75, 150.04 (dd, J c - p = 15.6 and 14.2 Hz), 152.37 (dd, Jc-p = 8.7 and 7.9 Hz); 31PN M R (81 MHz, CDC13) 6 -42.7. Anal. Calcd for C40H36Fe204P2: C, 63.69; H, 4.81. Found: C, 63.39; H, 4.63.
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132.35 (t, 1'Jp-c 3 J ~ -=~ 43.3 I Hz, ipso), 133.40 (t, I2Jp-c + 4Jp-cI = 9.6 Hz, ortho), 137.55 (t, I2Jp-c + 4Jp-cI = 11.4 Hz, ortho); 31PNMR (81 MHz, CDCl3) 6 29.92. Anal. Calcd for CaH~BrzFezP2Pd: C, 54.35; H, 4.18. Found: C, 54.27; H, 4.03.
trans-[PdCl2{ (R,R)-(S,S)-Ph'l"}l(8). To a suspension of [PdC12(CH&N)zI (8.0 mg, 0.031 mmol) in CH2Cl2 (0.5 mL) was added a solution of (RP)-(S,S)-la (24.4 mg, 0.031 mmol) in CHzCl2 (0.5 mL) at room temperature. The orange solution was stirred for 30 min. The product was purified by silica gel chromatography (CH2ClfltOAc = 20/1): yield, 27.3 mg (92%); orange crystals; mp 230-235 "C (decomp); [aI2O~ -726 (c 0.55, CHCl3); 'H NMR (200 MHz, CDC13) 6 1.66 (td, I3JP-H + 5JP-HI = 12.0 and IJH-H/ = 7.2 Hz, 6 H), 3.72 ( d d , J = 2.5 and 1.4Hz, 2 H), 4.08 (tq, I 2 J p - ~ 4JP-HI = 6.8 and /JH-H/ = 7.2 Hz, 2 H), 4.31 (s, 10 H), 4.42 (t, J = 2.5 Hz, 2 H), 4.67 (dd, J = 2.5 and 1.4 Hz, 2 H), 7.2-7.4 (m, 16 H), 7.9-8.0 (m, 4 H); 13C NMR (50 MHz, CDCl3) 6 19.88, 30.90 (t, 1'Jp-c + 3Jp-c/ = 18.3 Hz), 67.61,68.06, 70.14 (Cp), 72.74,86.68,91.71 (t, 12Jp-c + 4J~-cI = 9.6 Hz), 127.08 (t, I3Jp-c 5J~-~I = 9.7 Hz, metal, 127.23 (t, I3Jp-c + 5 J ~ -=~9.0 I Hz, metal, 127.93 (t, 1lJp-c + 3 J ~ - ~ I = 38.5 Hz, ipso), 129.12 (para), 130.59 (para), 130.94 (t, 1lJp-c (R,R)-2-[(S)-l-(Diphenylphosphino)ethyl]-2"-[(S)-l-{bis- 3 J p - ~ l= 43.6 Hz, ipso), 133.46 (t, I2Jp-c + 4 J p - ~ I= 9.0 Hz, ortho), 137.80 (t, 12Jp-c 4Jp-cI = 10.6 Hz, ortho); 31PNMR (4-methylphenyl)phosphino}ethyl]-1,l"-biferrocene (le) (81 MHz, CDC13) 6 25.11. Anal. Calcd for C48H44ClzFezPzPd: was prepared as described for the preparation la: 90% yield; C, 59.32; H, 4.56. Found: C, 59.10; H, 4.54. f 4 0 5 (c 0.51, orange amorphous solid; mp 71-75 "C; [a125~ trans-[PdIz{ (R,R)-(S,S)-PhTRAP}l (9). To a suspension CHC13);'H NMR (500 MHz, CDCl3) 6 1.36 (pseudo-t, 6 H), 2.24 of PdIz (1.64 g, 4.55 mmol) in CH2Cl2 (20 mL) was added a (9, 3 H), 2.28 (9, 3 H), 3.44 (9, JH-H = 7 Hz, 1HI, 3.49 (9, JH-H solution of (R,R)-(S,S)-la (3.52 g, 4.43 mmol) in CHzClz (55 = 7 Hz, 1HI, 3.75 (m, 1HI, 3.82 (m, 1HI, 4.098 (t, JH-H = 2.4 mL) at room temperature. The deep orange solution was Hz, 1H), 4.103 (t, JH-H= 2.4 Hz, 1H), 4.29 (8,5 H), 4.30 (9, stirred for 40 min. After the remaining PdI2 was filtered off, 5 H), 4.54 (m, 1H), 4.56 (m, 1H), 6.88 (br d, 2 H), 6.98 (br d, the solvent was evaporated to give a crude product in quan2 H), 7.11-7.22 (m, 8 HI, 7.22-7.33 (m, 6 H); 13C NMR (125 titative yield. The product was purified by silica gel chromaMHz, CDCl3) 6 17.15 (d, 2Jp-c = 1.8 Hz), 17.55 (d, 2Jp-c = 3.3 tography (CH2C12): orange crystals; mp 160-165 "C (decomp); Hz), 21.13, 21.26 (d, 'Jp-c % 0.5 Hz), 29.04 (dd, Vp-c = 19.6 [ a I z 5-250 ~ (C 0.10, CHCl3); 'H NMR (200 MHz, CDC13) 6 1.58 and 2 J ~ = 2.1 - ~Hz), 29.06 (dd, V - C= 18.4 and 2 J ~ =2.6~ Hz), 65.25, 65.28, 68.08 (d, 3Jp-c = 6.8 Hz), 68.24 (d, 3Jp-c = = 7.3 Hz, 6 H), 4.03 (tq, (td, I3JP-H 5JP-HI = 12.4 and IJH-HI I 2 J p - ~ 4Jp-HI = 6.6 and IJH-HI = 7.3 Hz, 2 H), 4.07 (dd, JH-H 7.8 Hz), 69.25 (Cp),69.27 (Cp), 71.70 (d, 4Jp-c = 2.5 Hz), 71.78 = 2.6 and 1.4 Hz, 2 HI, 4.31 (s, 10 HI, 4.49 (t, IJH-HI = 2.6 Hz, (d, 4Jp-c = 2.7 Hz), 84.21 (d, 3Jp-c = 3.9 Hz), 84.38 (dd, 3Jp-c 2 H), 4.67 (dd, JH-H = 2.6 and 1.4 Hz, 2 H), 7.2-7.5 (m, 16 H), = 3.9 and 4Jp-c = 0.5 Hz), 93.12 (d, 2Jp-c = 19.5 Hz), 93.45 7.7-7.8 (m, 4 H); 13C NMR (50 MHz, CDC13) 6 19.69, 36.35 (t, (d, 2 J p - ~= 19.6 Hz), 127.11 (d, 4 J p - ~= 0.5 Hz, para), 127.47 (d, 3 J ~ = -6.8~Hz, metal, 128.00 (d, 3 J ~ = -4.5~Hz, metal, I'JP-c + 3J~-cI= 19.3 Hz), 67.31, 69.15, 69.95 (Cp), 74.00, 86.27, 91.64 (t, I3Jp-c + 5Jp-cI = 8.6 Hz), 126.81 (t, I3Jp-c + 128.34 (d, 3 J p - ~= 6.8 Hz, metal, 128.44 (d, 4 J p - ~ 0.5 Hz, =~10.0 I Hz, metal, 127.23 (t, I3Jp-c + 5 J ~ -= ~ I9.5 Hz, = -4.9~Hz, metal, 132.05 (dd, 2 J ~=- ~ 5 J ~ para), 128.77 (d, 3 J ~ -~ 40.2 I Hz, ipso), 129.51 (para), meta), 129.29 (t, 1'Jp-c 3 J ~= 16.1 and 3 J p - ~= 1.9 Hz, ortho), 132.10 (dd, 2 J p - ~= 16.6 and 130.62 (para), 133.43 (t, I2Jp-c + 4 J ~ - ~ I = 9.9 Hz, ortho), 135.45 3J~ = 2.2 - ~Hz, ortho), 132.91 (d, VP-C= 20.0 Hz, ipso), 135.08 (t, 1lJp-c 3 J p - ~ I= 44.1 Hz, ipso), 137.23 (t, I2Jp-c 4 J ~ = -~I (dd, 2 J p - ~= 19.5 and 3 J p - ~= 2.4 Hz, ortho), 135.29 (dd, 2 J p - ~ 11.3 Hz, ortho); 31PNMR (81 MHz, CDC13) 6 27.82. Anal. = 19.5 and 3 J ~ = -2.5~Hz, ortho), 135.55 (dd, 'JP-c = 18.3 Calcd for CaHGe212P2Pd: C, 49.93; H, 3.84. Found: C, 49.90; and 2 J p - ~= 1.7 Hz, ipso), 136.01 (d, Vp-c = 21.4 Hz, ipso), H, 3.76. 136.80 (d, 4 J ~ = -0.5~Hz, para), 138.22 (d, 4 J ~= -0.5~Hz, para), 139.05 (dd, 9p-c = 20.2 and 2 J p - ~= 1.5 Hz, ipso); 31P trun~-[PtCl~{(R,RR)-(S,S)-PhTRAP}l (trans-10). To a NMR (81 MHz, CDC13) 6 0.40 and 2.58 (ABq, J = 22.0 Hz). suspension of [PtC12(CH&N)21(17.3mg, 0.050 mmol) in CH2Anal. Calcd for C50H4sFezPz: C, 73.01; H, 5.88. Found: C, (39.8 mg, Cl2 (3 mL) was added a solution of (RP)-(S,S)-la 73.06; H, 6.01. 0.050 mmol) in CHzCl2 (2 mL) at room temperature. The orange solution was stirred at 40 "C for 30 min. The product truns-[PdBrz{ (S,S)-(R,R)-PhTRAP}l (7). To a suspenwas purified by silica gel chromatography (CHzC12) and sion of PdBrz (81.3 mg, 0.305 mmol) in CH2Cl2 (2 mL) was recrystallized from CH2C12/EtOH yield, 43.0 mg (82%); orange added a solution of (S,S)-(R,R)-la (200.0 mg, 0.252 mmol) in -571 (c 0.57, CHCl3); crystals; mp 240-245 "C (decomp);[aI2O~ CHzCl2 (2 mL) at room temperature. The deep orange solution 'H NMR (400 MHz, CDC13) 6 1.68 (td, I 3 J p - ~+ 5 J p - ~ I= 12.2 was stirred for 30 min. Afbr the remaining PdBr2 was filtered off, the resulting solution was concentrated. Ether was slowly and IJH-HI = 7.3 Hz, 6 H), 3.75 (dd, J = 2.4 and 1.4 Hz, 2 H), added to the solution, and the orange precipitate that formed 4.06 (tq, I 2 J p - ~+ 4 J ~ - ~ I = 7.3 and IJH-HI = 7.3 Hz, 2 HI, 4.31 (s, 10 H), 4.39 (t, J = 2.4 Hz, 2 H), 4.64 (dd, J = 2.4 and 1.4 was collected and dried in vacuo: yield, 237.4 mg (89%); orange Hz, 2 H), 7.23-7.42 (m, 16 H), 7.83-7.90 (m, 4 HI; 13C NMR crystals; mp 250-255 "C (decomp); [ a I 2 O ~+644 (c 0.232, CHC13); 'H NMR (200 MHz, CDC13) 6 1.68 (td, I3JP-H + 5JP-HI (100 MHz, CDCl3) 6 19.99, 30.89 (t, I'Jp-c + 3Jp-cI = 28.1 Hz), 67.08, 67.82, 69.65 (Cp), 72.51,86.57,91.64 (t, I2Jp-c + 4J~-cI = 12.0 and IJH-HJ = 7.2 Hz, 6 H), 3.92 (dd, JH-H= 2.4 and 1.4 Hz, 2 H), 4.10 (tq, I 2 J p - ~+ 4 J p - ~ I= 7.1 and J H-HI = 7.2 Hz, = 7.3 Hz), 127.03 (t, 1lJp-c + 3J~-~I = 46.3 Hz, ipso), 127.07 (t, I3Jp-c 5J~-~I = 9.8 Hz, metal, 127.26 (t, I3Jp-c + 5 J ~ - ~ I = 2 HI, 4.32 (9, 10 HI, 4.43 (t, IJH-HI = 2.4 Hz, 2 HI, 4.66 (dd, 10.7 Hz, metal, 129.90 (para), 129.94 (t, 1lJp-c + 3 J ~ = -~ 50.1 I JH-H = 2.4 and 1.4 Hz, 2 H), 7.2-7.5 (m, 16 H), 7.8-7.9 (m, 4 H); 13CNMR (50 MHz, CDC13) 6 20.38,33.25 (t, I'JP-c + 3J~-cI Hz, ipso), 130.61 (para), 133.51 (t, lZJp-c + 4J~-cI = 9.8 Hz, ortho), 137.56 (t, I2Jp-c + 4Jp-cI = 11.0 Hz, ortho); 31PNMR = 19.2 Hz), 67.24, 68.36, 69.81 (Cp), 73.10, 86.22, 91.77 (t, (81 MHz, CDC13) 6 21.41 (t, Jlgspt-3ip = 2612 Hz). Anal. Calcd I2Jp-c + 4J~-cI= 9.2 Hz), 126.97 (t, I3Jp-c + 5Jp-cI = 10.1 Hz, for C48H44C12Fe2P2Pt: C, 54.36; H, 4.18. Found: C, 54.06; H, = 9.1 Hz, metal, 127.83 (t, meta), 127.13 (t, I3Jp-c 5J~-~I 4.04. I'JP-c + 3J~-cI= 39.4 Hz, ipso), 129.25 (para), 130.58 (para),
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Trans-Chelating Chiral Diphosphine Ligands
Organometallics, Vol. 14, No. 10,1995 4557
ciS-CptClz{(R,R)-(S,S)-PhTRAP}l (cis-lo). After the trans2.4Hz, para), 130.75(d, 4 J ~=-2~ .4Hz, para), 131.44(dd, 2 J ~ - ~ 10 was eluted by silica gel chromatography described above, = 8.6and 4 J p - ~= 1.0Hz, ortho), 133.62(dd, 2 J p - ~= 8.0 and cis-10 was eluted with CH2C12/acetone (9/1):orange powder; 4 J p - ~= 1.4Hz, ortho), 135.56(d, Vp-c = 46.4Hz, ipso), 136.74 'H NMR (200MHz, CDC13) 6 0.7-0.9(m, 6 H), 3.74(m, 2 H), (dd, 2 J ~=- 10.4 ~ and 4 J ~=- 1~.8Hz,ortho), 137.49(dd, 2 J ~ - ~ 3.88(9, 10 H), 4.42(m, 2 H), 4.87(m, 2 H), 7.2-7.4(m, 12H), = 9.1and 4 J ~=- 1.8 ~ Hz, ortho), 172.74(t, 2 J ~=- 1~0.7Hz, 7.5-7.6(m, 4 H), 7.9-8.0(m, 4H); 31PNMR (81MHz, CDC13) CO); 31PNMR (81MHz, CDC13) 6 21.00(d, J = 343.9Hz), 6 16.12(t, J l S S p t - 3 1 ~ = 3668 Hz). 40.41(d, J = 343.9Hz); IR (KBr)1960cm-'. Anal. Calcd for C4gH&lFe21rOP~: C, 56.04; H, 4.22.Found: C, 55.88; H, 4.14. truns-[PtCl~((S,S)-(R,RR)-le}l (11). To a suspension of [PtClz(CH3CN)21(10.4mg, 0.0299mmol) in CHzCl2 (0.6mL) truns-[RhCl(CO){ (S,S)-(R&)-PhTRAP}I (13). To a soluwas added unsymmetrical TRAP (S,S)-(RP)-le(24.7mg, tion of [{Rh(CO)2}2@-C1)~1 (48.3mg, 0.124mmol) in 5 mL of 0.0300mmol) at room temperature. The orange solution was CH2Cl2 was added ( S , S ) - ( R P ) - l ( a202.3mg, 0.255mmol) at stirred at 35 "C for 30min. The product was purified by silica room temperature, and the mixture was stirred for 10 min. gel chromatography (CH2C12) and recrystallized from CH2C12/ The solution was diluted with EtOH, and most of CH2C12 was EtOH in high yield: orange powder; mp 235-240 "C (decomp); evaporated. Orange crystals were collected and dried in vacuo [aI2O~+594 (c 0.56, CHC13); 'H NMR (500MHz, CDC13) 6 1.656 to give 217.8mg (92%)of trans-13: mp 230-235 "C (decomp); (dd, JP-H = 12.2and JH-H = 7.5Hz, 3 H), 1.665(dd, J p - H = [aI2'~ +700 (C 0.52, CHCl3); 'H NMR (400MHz, CDC13) 6 1.59 12.0and JH-H = 7.6Hz, 3 H), 2.327(s, 3 H), 2.333(8, 3 H), (dd, JP-H = 10.9and JH-H = 7.2Hz, 3 H), 1.61(dd, J p - H = 3.74(dd, JH-H = 2.5and 1.5Hz, 1 H), 3.76(dd, JH-H = 2.5 10.9and JH-H = 7.2Hz, 3 H), 3.39(ddd, JP-H = 1.4, JH-H = and 1.5Hz, 1 H), 4.03(m, 2 H, a-CH), 4.30(s, 10 H), 4.37(t, 2.5,and JH-H = 1.4Hz, 1 H), 3.68(ddd, JP-H = 1.4, JH-H = JH-H = 2.5Hz, 1 H), 4.38(t, JH-H = 2.5Hz, 1 H), 4.62(dd, 2.5,and JH-H = 1.4Hz, 1 HI, 3.85(dq, JP-H = 5.3and JH-H = JH-H = 2.5and 1.5Hz, 1 H), 4.63(dd, JH-H = 2.5and 1.5Hz, 7.2Hz, 1 H), 4.06(dq, JP-H = 6.7and JH-H = 7.2Hz, 1 H), 1 H), 7.06(pseudo-d, 2 H), 7.11(pseudo-d, 2 H), 7.18(ddd, 2 4.26(s, 5 H), 4.29(s, 5 H), 4.33(t, J = 2.5Hz, 1 H), 4.38(t, J H), 7.26(pseudo-t, 2 H), 7.31(m, 5 H), 7.39(pseudo-t, 1 H), = 2.5Hz, 1 H), 4.58(dd, J = 2.5and 1.4Hz, 1 H), 4.63(dd, J 7.74(ddd, 2 H), 7.87(m, 2 H); 13C NMR (125MHz, CDC13) 6 = 2.5and 1.4Hz, 1 H), 7.23-7.46(m, 16 H), 7.48-7.55(m, 2 19.95(pseudo-d, I2Jp-c + 4 J p - ~ I = 1.5Hz), 19.98(pseudo-d, H), 7.96-8.03(m, 2 H); 13C NMR (100MHz, CDC13) 6 19.31 I2Jp-c + 4Jp-cI = 1.5Hz), 21.40,21.44,30.84 (dd, I'Jp-c (d, 'JP-c= 4.5Hz), 19.55(ddd, 2 J ~=- 4.3, ~ 3JRh-C = 1.3and = 26.9Hz), 30.91(t, I'Jp-c + 3Jp-cI = 26.9Hz), 67.03, 67.08, 4Jp-c = 1.3Hz), 32.05(d, 'Jp-c = 23.8Hz), 32.06(d, 'Jp-c = 67.78(t, I3Jp-c + 'Jp-cI or 14Jp-c %--cI = 2.2Hz), 67.90(t, 21.3Hz), 66.55,67.14 (d, 3 J ~ - = c 2.7Hz), 67.17,67.64 (d, Vp-c I3Jp-c + %7p-cI or I4Jp-c + %Tp-cI = 2.5Hz), 69.65(Cp, 10 C), = 2.4Hz), 69.50(Cp), 69.76(Cp), 71.96, 72.23, 86.15(d, 3Jp-c 72.42,72.49,86.58 (t, I3Jp-c + 'JP-CI= 1.5Hz), 86.64(t, I3Jp-c = 1.9Hz), 86.17(d, 3 J ~ - c= 1.8Hz), 92.07(d, 2Jp-c = 10.3 'Jp-cI = 1.5Hz), 91.69(dd, I2Jp-c + 4Jp-cI = 8.8Hz), 91.86 Hz), 92.71(d, 2Jp-c = 10.3Hz), 127.10(d, 'Jp-c = 8.5Hz, (dd, 12Jp-c 4Jp-ci = 8.2Hz), 123.54(dd, lilp-c = meta), 127.19(d, 3 J p - ~= 9.2Hz, meta), 127.27(d, Vp-c = 9.1 49.1Hz, ipso), 126.58(dd, 1'Jp-c + 3J~-~I = 52.5Hz, ipso), Hz, meta), 128.18(d, 3 J ~=- 8.0 ~ Hz, metal, 128.72(d, 4 J p - ~ 127.02(dd, I3Jp-c + 5 J ~ - = ~ I10.1Hz, meta), 127.24(dd, 1 V - c = 1.8Hz, para), 128.89(d, 4 J p - ~= 1.8Hz, para), 129.02(dd, + VP-CI= 45.2Hz, ipso), 127.23(dd, I3Jp-c + 5 J ~ - =~ I9.1Hz, 'JP-c= 24.4and 3 J p - ~= 7.9Hz, ipso), 129.43(ddd, lJp-c = metal, 127.86(dd, I3Jp-c 'Jp-cI = 10.4Hz, metal, 128.07 32.4,'JRh-c = 3.1,and 3Jp-c = 3.1Hz, ipso), 130.29(d, 4Jp-c = 2.4Hz, para), 130.62(d, 4 J p - ~= 2.5Hz, para), 131.49(d, (dd, I3Jp-c + 'Jp-cI = 9.4Hz, metal, 129.13(para), 130.01(dd, 2 J ~=- 9.1 ~ Hz, ortho), 131.52(dd, VP-C= 36.6and 3 J ~=- ~ I'JP-c + 3J~-cI = 50.1Hz, ipso), 130.54(para), 133.45(dd, 12Jp-c + 4Jp-cI = 9.7Hz, ortho), 133.53(dd, I2Jp-c + 4Jp-cI = 3.0Hz, ipso), 133.35(d, 2 J p - ~= 7.9Hz, ortho), 136.31 (dd, 9.8Hz, ortho), 137.48(dd, I2Jp-c + 4Jp-c) = 11.3Hz, ortho), 'JP-c= 37.0and 3 J p - ~= 1.8Hz, ipso), 136.85(ddd, 2 J ~=- ~ 137.60(dd, I2Jp-c + 4 J p - ~ I = 11.0 Hz, ortho); 139.16(para), 11.6, 3JRh-C = 1.6, and 4 J p - ~= 1.6Hz, ortho), 137.46(dd, 2 J p - ~ 140.78(para); 31PNMR (202MHz, CDC13) 6 20.68,21.38 (main = 9.8and 3J~h-c or 4Jp-c = 1.9HZ, ortho), 187.83(ddd, 'JRh-c peaks, ABq, J 3 1 p - q = 490 Hz, 70/1intensity; satellites, ABX = 174.5, 2 J p - ~= 17.1and 2 J p - ~= 13.4Hz, CO); 31PNMR (81 spin system, J 1 9 5 p t - 3 1 ~= 2550-2600 Hz and J 1 9 5 p t - 3 1 ~ = 2600MHz, CDCl3) 6 26.25(dd, 'J~h-p = 129.4and V p - p = 354.8 2650Hz). Anal. Calcd for C50&&12Fe2PzPt: C, 55.17; H, 4.44. Hz), 48.06(dd, ' J f i - p = 125.6and 2Jp-p = 354.8Hz); IR (KBr) Found: C, 55.11;H, 4.19. 1972cm-'. Anal. Calcd for C49H&lFe20P2Rh: C, 61.25; H, 4.62.Found: C, 61.04;H, 4.65. truns-[IrCl(CO){ (S,S)-(R,R)-PhTRAP}l (12). A solution of [IrCl(CO)2(p-toluidine)l(78.1mg, 0.200mmol) and (S,S)tr~ns-[RhCl(CO){(S,S)-(R,R)-FU~TRAP}](14). [{Rh@$?)-la (160.5mg, 0.202mmol) in CH2Cl2 (10 mL) was stirred (CO)2}2@-C1)21(16.8 mg, 0.043mmol) and ( S , S ) - ( R P ) - l(65.2 d at 40 "C for 10 min. The solvent was concentrated, and the mg, 0.086mmol) were dissolved in 1mL of CH2C12. After the residue was recrystallized from CHZCl&tOH to give 183.5mg evolution of carbon monoxide ceased, the solvent was evaporated. Recrystallization from CHZClDtOH gave 14 (85%)as (88%)of trans-12: orange crystals; mp 230-235 "C (decomp); +598 (c 0.54,CHCld; 'H NMR (400MHz, CDC13) 6 1.55 +560 (c 0.25, [aI2O~ orange crystals: mp 200-205 "C (decomp); [aI2O~ CHC13); 'H NMR (400MHz, CDC13) 6 1.79(dd, J p - H = 11.8 (dd, J p - H = 11.9and JH-H = 7.1Hz, 3 H), 1.65(dd, JP-H = and JH-H = 7.1Hz, 3 H), 1.88(dd, JP-H = 11.8and JH-H = 7.1 11.7and JH-H = 7.2Hz, 3 H), 3.40(m, 1 H), 3.66(m, 1 H), Hz,3 HI, 3.58(m, 1 H), 3.67(dq, JP-H = 4.5and JH-H = 7.3 3.89(dq, J p - H = 7.3and JH-H = 7.2Hz, 1 H), 4.05(dq, JP-H = Hz, 1 H), 3.77(dq, J p - H = 5.7and JH-H = 7.3Hz, 1 H), 3.84 7.3and JH-H = 7.1Hz, 1 H), 4.26(s, 5 H), 4.28(8,5 H), 4.34 (t,J=2.6Hz,lH),4.35(t,J=2.6Hz,lH),4.54(dd,J=2.6 (m, 1 H), 4.29(s, 5 H), 4.32(s, 5 H), 4.36(m, 1 H), 4.51(dd, and 1.4Hz, 1 H), 4.62(dd, J = 2.6and 1.6Hz, 1 H), 7.25JH-H = 2.5and 1.5Hz, 1H), 4.56(dd, JH-H = 2.5and 1.5Hz, 7.45(m, 16 H), 7.45-7.52(m, 2 HI, 7.98-8.03(m, 2 H); 13C lH),6.38(dt,J=3.3and1.5Hz,lH),6.41(ddd,J=3.4and NMR (100MHz, CDC13) 6 19.10(dd, 2 J ~=- 3.7 ~ and 4 J ~=- ~ 1.8Hz, 1.0Hz, 1 H), 6.45(dt, J = 3.6and 2.0Hz, 1 H), 6.48 1.8Hz), 20.14(dd, 2 J p - ~= 3.7and 4 J p - ~= 1.8Hz), 32.01(d, (ddd, J = 3.3, 1.5,and 1.3Hz, 1 H), 6.52(d, J = 3.4Hz, 1 H), 'Jp-c = 30.5Hz), 32.98(d, 'Jp-c = 30.0Hz), 66.38,67.02,67.28 6.86(dt, J = 3.4and 0.7Hz, 1 H), 6.98(ddd, J = 6.0, 1.8, and 0.7Hz,1 H), 7.60(m, 1 H), 7.63(m, 1 H), 7.68(m, 1 H), 7.71 (d, 3Jp-c = 2.4Hz), 67.72(d, 3Jp-c = 2.5Hz), 69.44(Cp),69.74 (Cp), 72.22,72.33,86.40(d, Vp-c = 1.8Hz), 87.02(d, Vp-c = (m, 1 H), 7.83(ddd, J = 6.0,1.8, and 0.7Hz, 1 H); 13C NMR 1.9Hz),91.97(d, 2Jp-c = 8.6Hz), 92.33(d, 2Jp-c = 8.6Hz), (100MHz, CDCl3) 6 19.93(dt, J = 5.6and 1.0Hz), 20.15(ddd, 127.17(d, 3 J p - ~= 9.2Hz, meta), 127.22(d, 3 J p - ~= 9.7Hz, J = 5.8,1.7, and 0.8 Hz),34.88(d, J = 26.0Hz),36.12(d, J = 25.9Hz), 66.32(d, J = 3.9Hz), 67.13(s), 67.38(s), 67.52(d, J metal, 127.24(d, Vp-c = 9.2Hz,meta), 128.01(d, 3 J p - ~= 9.2 Hz, meta), 128.25(dd, 'Jp-c = 41.1and 3 J p - ~= 3.0Hz, ipso), = 3.0Hz),69.55(s), 69.75(s), 71.02(s), 71.52(s), 85.58(d, J = 2.3Hz), 86.04(d, J = 2.3 Hz), 90.89(d, J = 9.9Hz), 92.40 128.98(d, 4 J p - ~= 2.1Hz, para), 129.10(dd, V p - c = 32.4and (d, J = 10.7Hz),110.67(d, J = 5.0 Hz), 110.74(d J = 3.5Hz), 3 J p - ~= 7.4Hz, ipso), 129.15(d, 4 J p - ~= 2.5Hz,para), 130.41 111.17(s), 111.24(s), 119.69(d, J = 2.6Hz),122.43(dd, J = (dd, V - C= 42.8and 3 J p - ~= 2.4Hz,ipso), 130.45(d, 4 J p - ~=
+
+
+
+
+
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Sawamura et al.
4558 Organometallics, Vol. 14,No. 10, 1995
Table 4. Summary of Crystal Data and Details of Data Collection and Refinement Parameters for 7 and 14CHzC12 complex formula fw cryst syst space group a
(A)
c
(8)
b (A)
a (de& p (deg) (deg)
v (A31
14CHzC12 C ~ ~ H ~ ~ B I - ~ FC4~H3805C13FezP2Rh ~ZPZP~ 1060.78 1005.67 monoclinic triclinic P21 (NO.4) P1 (No. 1) 12.778(6) 10.593(2) 9.917(7) 19.665(2) 17.458(4) 10.582(2) 102.86(1) 103.79(2) 107.51(1) 81.36(1) 2041.2(6) 2148(1) 7
2
2
2
D(ca1cd)(g/cm3) cryst size ("3) p(Mo Ka) (cm-l) scan type scan rate (deglmin) scan width (deg) 28 range (deg) no. of measd reflns no. of unique reflns no. of obsd reflns (Z > 3.00a(Z)) no. of variables R
1.640 0.30 x 0.20 x 0.15 30.53 w-28 8.0 1.15 + 0.30 tan 8 3-60 6866 6603 (Rint = 3.80) 3441
1.636 0.50 x 0.25 x 0.20 14.18 0,-28 8.0 1.37 + 0.30 tan 8 3-60 12489 11890 (Rint = 0.018) 10071
496 0.047 0.061 1.99 0.01
1062 0.032 0.036 1.55 0.22
1.06
0.71
-0.75
-0.72
RW
S max shiwerror in final cycle maximum peak in diff Fourier map (e/A3) minimum peak in diff Fourier map (e1A3)
14.5 Hz, 1.6 Hz), 125.39 (d, J = 17.2 Hz), 129.19 (d, J = 20.6 Hz), 142.30 (ddd, J = 34.2, 13.7, and 1.4 Hz), 144.90 (dd, J = 52.3 and 7.3 Hz), 145.65 (ddd, J = 48.0,6.6, and 3.5 Hz), 146.38 (d, J = 4.2 Hz), 146.71 (d, J = 4.6 Hz), 147.12 (d, J = 2.7 Hz), 147.49 (d, J = 3.8 Hz), 147.95 (ddd, J = 58.4, 2.5 and 1.7 Hz), 184.83 (ddd, J = 72.5, 18.2, and 14.9 Hz); 31PNMR (81 MHz, CDC13) 6 4.5 (dd, l J ~ h - p= 134.9 and V p - p = 394.0 Hz), 12.3 (dd, 'Jp.h-p = 133.3 and 2 J p - p = 394.0 Hz). Anal. Calcd for C41H3&1Fe205P2RhCH&lz: C, 50.16; H, 3.61. Found: C, 50.06; H, 3.65. X-ray Crystal StructureAnalysis of 7. Suitable crystals for diffraction study were grown by slow diffusion of ethanol into a CH2Cl2 solution of 7 at 4 "C. The data were collected a t 20 "C on a Rigaku AFC7R diffractometer with graphitemonochromated Mo K a radiation. Cell constants and an orientation matrix for data collection were obtained from a least-squares refinement using the setting angles of 25 carefully centered reflections in the range of 24.45 < 28 < 28.25". The intensities of three standard reflections monitored every 150 reflections showed no serious decay. All data were corrected for Lorentz and polarization effects but not for
absorption. A correction for secondary extinction was applied (coefficient = 9.56834 x lo-'). A summary of cell parameters, data collection conditions, and refinement results is given in Table 4. The initial positional parameters of palladium atoms were determined by the direct method (MITHRILSO). Subsequent difference Fourier synthesis located all non-hydrogen atoms (DIRDIF), which were refined anisotropically. All hydrogen atoms were located in calculated positions (d(C-H) = 0.95 A), and their isotropic temperature factors were set equal to Be, of the carbon atoms to which they were attached. All hydrogen atoms were included but not refined. All calculations were performed using the t X s a n crystallographic software package. X-ray Crystal Structure Analysis of 14cH&12. Suitable crystals for diffraction study were grown by slow diffusion of ethanol into a CHzClz solution of 14 at 4 "C. The data were collected a t 20 "C on a Rigaku AFC7R diffractometer with graphite-monochromatd Mo Ka radiation. Cell constants and an orientation matrix for data collection were obtained from a least-squares refinement using the setting angles of 25 carefully centered reflections in the range of 38.65 < 20 < 39.57'. The intensities of three standard reflections monitored every 150 reflections showed no serious decay. All data were corrected for Lorentz and polarization effects but not for absorption. A summary of cell parameters, data collection condition, and refinement results is given in Table 4. Cell parameters suggested that each unit cell contained a set of two independent molecules. The initial positional parameters of two rhodium atoms were determined by the direct method (SAPI91). Subsequent difference Fourier synthesis located all non-hydrogen atoms (DIRDIF), which were refined anisotropically. All hydrogen atoms were located in calculated positions (d(C-H) = 0.95 A),and their isotropic temperature factors were set equal t o Be, of the carbon atoms t o which they were attached. All hydrogen atoms were included in fixed positions, and their isotropic thermal parameters were refined. Two independent molecules have almost the same structure except for the positions of oxygen atoms in fury1 groups on phosphorus atoms. All calculations were performed using the teXsan crystallographic software package.
Acknowledgment. We thank Mr. Tomohito Asai and Mr. Masaki Sudo for their efforts o n the preparation of phosphine ligands and complexes. Supporting Information Available: Details of full assignment of 'H and 13CNMR spectra of la with copies of 2D NMR spectra (I3C-'H HETCOR, 13CINADEQUATE, 13C-lH HMBC), copies of lH and I3C{lH} NMR spectra of 6b,e;tables of atomic coordinates, BlsJBeq,anisotropic displacement parameters, and bond lengths and bond angles for 7 and 14; ORTEP drawing of 14 (38 pages). This material is contained in libraries on microfiche, immediately follows this article in the microfilm version of the journal, and can be ordered from the ACS; see any current masthead page for ordering information. OM9502121
