Organometallics 1995, 14, 4825-4831
4825
Synthesis of New Butadiene-Osmium(0) and -Ruthenium(O) Complexes by Reductive Carbon-Carbon Coupling of T w o Alkenyl Fragments Cristina Bohanna, Miguel A. Esteruelas,* Fernando J. Lahoz, Enrique Ofiate, Luis A. Oro, and Eduardo Sola Departamento de Quimica Inorgcinica, Instituto de Ciencia de Materiales de Aragbn, Universidad de Zaragoza-Consejo Superior de Investigaciones Cientificas, 50009 Zaragoza, Spain Received May 10, 1995@ The five-coordinate complexes Os{ (E)-CH=CHR)Cl(CO)(PiPrs)z (R = Ph (3))H (6)) react (R = Ph with CH2=CHMgBr to give the osmium(0) derivatives OS(~~~-C~H~R)(CO)(P~P~~)~ (51, H (7)). The molecular structure of 5 has been determined by X-ray crystallography. The coordination around the osmium atom can be described as a distorted square pyramid with a triisopropylphosphine ligand located at the apex. The base is formed by the carbonyl group and the other triisopropylphosphine ligand mutually cis disposed and by the midpoints of both terminal carbon-carbon bonds of the diene. The reaction of the chloro-styrylruthenium(I1) complex Ru{ (E)-CH==CHPh}Cl(CO)(PiPr3)2 (4) with CHZ=CHMgBr leads to RU{(E)-CH=CHP~}(CH=CHZ)(CO)(P~P~~)Z (lo), which affords Ru(ll4-C4H5Ph)(CO)(PiPr3)2 (11) by stirring in hexane at 50 "C. 10 reacts with carbon monoxide to give Ru{(E)CH=CHPh}(CH=CHd(C0)2(PiPr3)2(121,which can be also prepared by reaction of Ru{(E)CH=CHPh}CI(C0)2(PiPr3)2 (13) with CH2'CHMgBr.
Introduction The reactions of alkynes with transition-metal hydrido complexes generally lead to vinyl derivatives.l The five-coordinate complexes MHCl(CO)(PiPr3)2(M = Os (1))Ru (2)) follow this trend. Thus, the reactions of 1 and 2 with phenylacetylene afford the corresponding styryl derivatives M{ (E)-CH=CHPh}Cl(CO)(PiPr3)2 (M = Os (31,Ru (4)12The most remarkable features of the structure of these compounds are, first, the square pyramidal coordination of the metal with the styryl ligand in the apical position and, second, the trans position of the two substituents-the phenyl group and the metallic fragment-at the carbon-carbon double bond. From a catalytic point of view, it has been proved that 3 is a key intermediate in the selective hydrogenation of phenyla~etylene,~ and 3 and 4 are side products in the catalytic hydrosilylation of phenylacetylene with triethyl~ilane.~ Continuing with our study on the chemical properties Of 3 and 4, we have now investigated the reactivity of 3 and 4 toward CHz=CHMgBr. During this research, we have found that the reactions of 3 and 4 with CHz=CHMgBr lead to n-(phenyllbutadiene complexes. Transition-metal butadiene complexes previously reported have been generally prepared by reducing a metal halide or halo complex in the presence of butadiene,5 by thermal or photolytic ligand displacement,'j Abstract published in Advance ACS Abstracts, September 15,1995. (1)Crabtree, R. H. The Organometallic Chemistry ofthe Transition Metals; J. Wiley and Sons: New York, 1988;pp 147-162. (2)Werner, H.; Esteruelas, M. A.; Otto, H. Organometallics 1986, 5,2295. (3)Andriollo, A,; Esteruelas, M. A.; Meyer, U.; Oro, L. A.; ShnchezDelgado, R.; Sola, E.; Valero, C.; Werner, H. J. Am. Chem. SOC.1989, 111, 7431. (4)(a)Esteruelas, M. A.; Oro, L. A.; Valero, C. Organometallics 1991, 10,462.(b) Esteruelas, M. A,; Herrero, J.; Oro, L. A. Organometallics 1993,12,2377. @
by metal atom evaporation techniques,' and by reaction of halo complexes with butadienylmagnesium derivatives.* The reductive coupling of two vinyl fragments to give a n-butadiene complex is rare, and previously, it has been only observed on ~irconium.~ The formation of carbon-carbon bonds at transitionmetal centers has received a great deal of attention in recent year^.^-^^ Catalytic systems involving transition metal complexes often form a carbon-carbon bond ( 5 ) (a) Hoberg, H.; Jenni, K, Raabe, E.; Kriiger, C.; Schroth, G. J. Organomet. Chem. 1987,320,325.(b) Diamond, G. M.; Green, M. L. H.; Walker, N. M.; Howard, J. A. K; Mason, S. A. J. Chem. Soc., Dalton Trans. 1992,2641. (6)(a) Ashworth, T. V.; Singleton, E.; Laing, M.; Pope, L. J. Chem. SOC..Dalton Trans. 1978. 1032.(b) Erker. G.: Wicher, J.: Enael, K.: Rosenfeldt, F.; Dietrich, W.; Kriiger, C. J.Am.' Chem. Soc.' 19&, 102; 6344.( c ) Kotzian, M.; Kreiter, C. G.; Michael, G.; Ozkar, S. Chem. Ber. 1983,116,3637.(d) Biich, H.M.; Binger, P.; Goddard, R.; Kriiger, C. J.Chem. SOC.,Chem. Commun. 1983,648.(e) Kreiter, C. G.; Kotzian, M. J. Organomet. Chem. 1985,289,295. (0 Kreiter, C. G.; Wendt, G.; Sheldrick, W. S. J. Organomet. Chem. 1987,333,47.(g) Green, M. L. H.; Hare, P. M.; Bandy, J. A. J. Organomet. Chem. 1987,330,61.(h) Fryzuk, M. D.; Joshi, K.; Rettig, S. J. Polyhedron, 1989,8, 2291.(i) Kreiter, C. G.; Kern, U. J.Organomet. Chem. 1993,459,199. (i) Blake, A. J.; Halcrow, M. A.; Schrijder, M. J.Chem. SOC.,Dalton Trans. 1994, 1631. (7)Brown, P. R.;Green, M. L. H.; Hare, P. M.; Bandy, J. A. Polyhedron 1988,7, 1819. (8)(a) Oro, L. A. Inorg. Chim. Acta 1977,21,L6.(b) Wreford, S. S.; Whitney, J. F. Inorg. Chem. 1981,20,3918.( c ) Yasuda, H.; Tatsumi, K.; Okamoto, T.; Mashima, K.; Lee, K.; Nakamura, A.; Kai, Y.; Kanehisa, N.; Kasai, N. J.Am. Chem. SOC.1985,107,2410. (d) Mtiller, J.;Qiao, K ; Siewing, M.; Westphal, B. J. Organomet. Chem. 1993,458, 219. (9)(a) Beckhaus, R.;Thiele, K.-H. J. Organomet. Chem. 1984,268, C7. (b) Czisch, P.; Erker, G.; Korth, H.-G.; Sustmann, R. Organometallics 1984,3,945. (10)(a) Kurosawa, H.; Emoto, M.; Ohnishi, H.; Miki, K; Kasai, N.; Tatsumi, K.; Nakamura, A. J. Am. Chem. SOC.1987,109,6333. (b) Kurosawa, H.; Ohnishi, H.; Emoto, M.; Kawasaki, Y.; Murai, S. J.Am. Chem. SOC.1988,110,6272.( c ) Bianchini, C.; Graziani, M.; Kaspar, J.; Meli, A,; Vizza, F. Organometallics 1994,13,1165. (11)Negishi, E.; Takahashi, T.; Baba, S.; Van Horn, D. E.; Okukado, N. J.Am. Chem. SOC.1987, 109,2393. (12)Brady, C.; Pettit, R. J.Am. Chem. SOC.1980,102,6181. (13)Amatore, C.; Jutand, A. Organometallics 1988,7, 2203.
0276-733319512314-4825$09.00100 1995 American Chemical Society
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4826 Organometallics, Vol. 14, No. 10, 1995
Table 1. Selected Bond Lengths (A)and Angles (deg) for the Complex Os(l14-C4HSPh)(CO)(Pi~~)2
C1281
(5)"
os-P( 1)
os-P(2)
os- C( 1) Os-C(2) Os-C(3) Os-C(4) P(l)-Os-P(2) P(l)-Os-M(l)
P(l)-Os-M(2) CIS1
P(l)-OS-C(11) P(2)-Os-M(1) P(2)-0s-M(2) P(2)-0s-C(11)
2.3806(8) 2.3768(9) 2.246(3) 2.193(3) 2.184(3) 2.259(3) 108.75(3) 94.41(9) 137.83(9) 85.4(1) 118.4(1) 112.73(9) 96.4(1)
os-C(11) C(l)-C(2) C(2)-C(3) C(3)-C(4) C(11)-0
1.861(3) 1.453(5) 1.411(4) 1.441(5) 1.167(4)
M(l)-Os-M(2) M(l)-Os-C(ll) M(2)-Os-C(11) C(l)-C(2)-C(3) C(2)-C(3)-C(4) C(3)-C(4)-C(5) OS-C(ll)-O
59.3(1) 142.8(1) 97.0(1) 117.2(3) 117.5(3) 120.2(3) 175.8(3)
M(1) and M(2) represent the midpoints of the C(l)-C(2) and C(3)-C(4) olefin double bonds, respectively.
Figure 1. ORTEP view of the molecular structure of Os(7;14-C4H~Ph)(CO)(PiPr3)2 (5). through alkyl-acyl conversions with carbon m0n0xide.l~ There exist also increasing examples of carbon-carbon bond formation through reductive-elimination react i o n ~ In . ~ addition, ~ the desire to develop new methods for carbon-carbon bond formation of use in organic synthesis has spurred many such investigations. In this respect, numerous examples of the migratory insertion (14) (a) Parshall, G. W. Homogeneous Catalysis; J. Wiley and Sons: New York, 1980. (b) Masters, C. Homogeneous Transition Metal Catalysis; Chapman and Hall: London, 1981. (c) Atwood, J. D. Inorganic and Organometallic Reaction Mechanisms; BrooWCole: Mill Valley, CA, 1985. (15) (a) Thorn, D. L; Tulip, T. H. Organometallics 1982,1, 1580. (b) Thorn, D. L. Organometallics 1985,4, 192. (c) Komiya, S.; Shibue, A. Organometallics 1985,4, 684. (d) Komiya, S.; Ishikawa, M.; Ozaki, S. Organometallics 1988, 7, 2238. (e) Himmel, S. E.; Young, G. B. Organometallics 1988, 7, 2440. (0 Thaler, E. G.; Folting, K.; Caulton, K. G. J.Am. Chem. SOC.1990,112,2664. (g) Thompson, J. S.; Atwood, J. D. organometallics 1991, 10, 3525. (h) Goldberg, K. I.; Yang, J. Y.; Winter, E. L. J.Am. Chem. SOC.1994, 116, 1573. (16) Selnau, H. E.; Merola, J. S.J.Am. Chem. Soc. 1991,113,4008. (17) (a) Dobson, A.; Moore, D. S.; Robinson, S. D.; Hursthouse, M. B.; New, L. Polyhedron 1986,4,1119. (b) Jia, G.; Reingold, A. L.; Meek, D. W. Organometallics 1989, 8, 1378. (c) Field, L.; George, A. V.; Hambley, T. W. Inorg. Chem. 1990, 29, 4565. (d) Bianchini, C.; Peruzzini, M.; Zanobini, F.; Frediani, P.; Albinati, A. J. Am. Chem. SOC.1991, 113, 5453. (e) Wakatsuki, Y.; Yamazaki, H.; Kumegawa, N.; Satoh, T.; Satoh, J. Y. J. Am. Chem. SOC.1991,113, 9604. (0 Jia, G.; Gallucci, J. C . ; Rheingold, A. L.; Haggerthy, B. S.; Meek, D. W. Organometallics 1991, 10, 3459. (g) Jia, G.; Meek, D. W. Organometallics 1991, 10, 1444. (h) Field, L. D.; George, A. V.; Malouf, E. Y.; Slip, I. H. M.; Hambley, T. W. Organometallics 1991, 10, 3842. (i) McMullen, A. K.; Selege, J. P.; Wang, J. G. Organometallics 1991,10, 3421. (i) Bianchini, C.; Bohanna, C.; Esteruelas, M. A,; Frediani, P.; Meli, A,; Oro, L. A,; Peruzzini, M. Organometallics 1992,11,3837. (k) Albertin, G.; Antoniutti, S.; Del Ministro, E.; Bordignon, E. J. Chem. Soc., Dalton Trans. 1992,3203. (1) Field, L. D.; George, A. V.; Purches, G. R.; Slip, I. H. M. Organometallics 1992, 11, 3019. (m) Santos, A,; Lbpez, J.; Matas, L.; Ros, J.; Galan, A,; Echavarren, A. M. Orgarwmetallics 1993,12,4215. (n) Hughes, D. L.; JimBnez-Tenorio, M.; Leigh, G. J.; Rowley, A. T. J. Chem. Soc., Dalton Trans. 1993, 3151. (0) Schafer, M.; Mahr, N.; Wolf, J.; Werner, H. Angew. Chem., Int. Ed. Engl. 1993, 32, 1315. (p) Wiedeman, R.; Steinert, P.; Schiifer, M.; Werner, H. J. Am. Chem. SOC.1993, 115, 9864. (q) Barbaro, C.; Bianchini, C.; Frediani, P.; Peruzzini, M.; Polo, A.; Zanobini, F. Inorg. Chim. Acta 1994, 220, 5. (18) (a) Brookhart, M.; Volpe, A. F., Jr.; Yoon, J. Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Ed.; Pergamon Press: London, 1991; Vol. 4, Section 3.5. (b) Chang, S.; Yoon, J.; Brookhart, M. J. A m . Chem. SOC.1994,116, 1869. (19) Carnahan, E. M.; Protascewicz, R. D.: Lippard. - _ S. J.ACC.Chem. Res. 1993,26, 90. (20) Liebeskind, L. S.: Chidambaram, R. J. A m . Chem. SOC.1987. 109, 5025. (21) OConnor, J. M.; Pu, L.; Rheingold, A. L. J. A m . Chem. Soc. 1990,112,6232. (22) Thorn, D. L.; Tulip, T. H. J.A m . Chem. SOC.1981, 103, 5984.
of vinylidene groups into metal-vinyl16 and metalalkynyl17bonds and the implications that such reactions may have for the catalytic alkyne oligomerization have been studied. Other pathways leading to carboncarbon bond formation which should be mentioned are the alkylation of (v3-allyl)ironcompounds,18the reductive-coupling of two isocyanide ligands to form a bis(alky1amino)acetylene the reaction of terminal alkynes with cobaltacyclopentenedione compounds to provide 5-alkylidene cyclopenten-2-ene-1,4-diene~,~~ the intramolecular coupling of two carbene ligands t o afford olefins,21and the alkyl migration from a metal atom to the carbon atom of a coordinated carbene ligand.22 In this paper, we describe the synthesis and characterization of new n-butadiene-osmium(0) and -ruthenium(0) compounds, which have been formed by the unusual coupling of two alkenyl fragments at the metallic center. Results and Discussion Treatment of 3 with CHz=CHMgBr in toluene gives a colorless solution from which compound 5 is separated as a white solid in 85% yield (eq 1). Complex 6 was fully characterized by elemental analysis, IR and IH, 31P{1H}, and 13C(lH} NMR spectroscopies, and X-ray diffraction. Ph
I hC// 'H C
3
PiPro
I
,Ph
5
Figure 1 shows an ORTEP drawing of the molecule of 5. Selected bond distances and angles are listed in Table 1. The geometry of this compound can be described as a square pyramid with a triisopropylphosphine ligand located a t the apex. The atoms C(11) and P(1) and the midpoints of the bonds C(l)-C(2) and C(3)-C(4) form the base and are approximately in one plane (maximum deviation 0.098(3) A), whereas the osmium atom is located 0.6832(5) A above this plane toward the apical position. The most conspicuous features of the solid state structure are those related to the 0~(7;1~-C4HsPh) unit. The osmium-carbon(t"l) distances (Os-C(l), 2.246(3) A; Os-C(4) = 2.259(3) A) are significantly longer
Butadiene-040) and -Ru(O) Complexes
Organometallics, Vol. 14, No. 10, 1995 4827
Scheme 1
II
I
than the osmium-carbodcentral) distances (Os-C(2), 2.193(3) A; Os-C(3), 2.184(3) A). Both carbon(termina1)-carbodcentral) distances (C(l)-C(2), 1.453(5) A; C(3)-C(4), 1.441(5)A) are also longer than the carbon(central)-carbodcentral) distance (C(2)-C(3), 1.411(4)
A).
The type of bonding of cis-butadiene ligands to transition metals can be described in terms of resonance hybrids of the forms I (q4-n)and I1 (u2-n)(Scheme 1). In our complex the geometric data commented above generate some ambiguity: while all the separations observed between osmium and the carbon atoms are in the usual range for Os-olefin complexes, and also agree well with a structure of type I, on the other side, the C-C bond distances show a long-short-long pattern more adequate for a type I1 structure. In order to determine the relative contribution of the resonance forms I and I1 in a structure of this type of compound, the parameters 8, Ad and A1 have been defined.23 For a diene ligand labeled as the phenylbutadiene of 5, the parameter 8 is the dihedral angle between the C(1)M-C(4) and C(l)-C(2)-C(3)-C(4) planes, while the parameters Ad and A1 can be calculated from the eqs 2 and 3, .respectively.
Ad = {d[M-C(l)]
+ d[M-C(4)1}/2
- {d[M-C(2)]
+
d[M-C(3)11/2 (2)
AI = {Z[C(l)-C(Z)]
+ Z[C(3)-C(4)1}/2
- Z[C(2)-C(3)]
(3) For the vast majority of middle and late transition metal diene complexes, which generally were assumed to adopt the q4-nstructure, the dihedral angle 8 is in the range 75-90', Ad is between -0.1 and 0.1 A, and A1 lies between -0.1 and 0 A. On the other hand, for the complexes of the early transition metals, which show a u2-n structure, the corresponding dihedral angles always exceed go', with a corresponding chan e in Ad of -0.4 to 0 A. A1 falls in the range 0-0.2 i!.23 The values obtained for complex 5 are 8 = 83.0(1)', Ad = 0.064(3) A, and A1 = 0.036(5) A. On the basis of the above mentioned criteria, 5 appears to be approaching the crossover between I and I1 assignments, suggesting a structure involving predominantly q4-ncoordination but with significant u2-ncontribution. The lH,13C{'H}, and 31P{1H} NMR spectra are in agreement with the structure shown in Figure 1. The protons of the diene ligand give rise to five signals at 5.16, 5.03, 1.94, 1.32, and -0.22 ppm (Figure 21, which were assigned t o the protons d, c, b, e, and a,respectively. The values of J a b = 3.9 and J a , = J b c = 6.9 Hz are consistent with a significant contribution of the resonance form I1 to the real structure of 5.24 In the 13C{IH} NMR spectrum the carbon atoms of the diene (23)Yasuda, H.; Nakamura, A. Angew. Chem., Int. Ed. Engl. 1987, 26,723. (24)(a) Benn, R.;Schroth, G. J . Organomet. Chem. 1982,228,71. (b) Brookhart, M.; Cox, IC;Cloke, F. G. N.; Green, J. C.; Green, M. L. H.; Hare, P. M.; Bashkin, J.; Derome, A. E.; Grebenik, P. D. J . Chem. Soc., Dalton Trans. 1985,423.
display four double doublets at 75.48 (Jp-c= 3.7 and 2.3 Hz), 71.98 (JP-c= 3.7 and 0.9 Hz), 44.80 (JP-c= 26.7 and 4.6 Hz), and 21.22 (JP-c= 5.6 and 3.2 Hz), which were assigned to the carbon atoms C(3), C(2), C(4), and C(l), respectively. In agreement with the mutually cis disposition of the triisopropylphosphine ligands the 31P{1H)NMR spectrum contains two doublets at 13.8 and 3.2 ppm, with a P-P coupling constant of 10.7 Hz. In a similar maner t o the chloro-styryl complex 3, the related chloro-vinyl compound Os(CH=CH,)Cl(CO)(PiPr& (6) reacts with CH2-CHMgBr to give the nbutadiene-osmium(0) derivative Os(q4-C4H6)(CO)(Pi&& (7) (eq 4), which was isolated as a white solid in 80% yield. H
I
HYc'H
PiPrl I
6
7
The structure of 7 is proposed on the basis of its lH, 13C{lH}, and 31P{lH} NMR spectra. Figure 3 shows the IH COSY NMR spectrum. The diene protons display six resonances at 5.05,4.56,1.71,1.64,-0.77, and -1.07 ppm. The resonances a t low field (5.05 and 4.56 ppm) were assigned to the internal protons i and h, respectively. The signals at 1.71 and 1.64 ppm were assigned to the syn-CH2 protons g and j, and the resonances a t higher field (-0.77 and -1.07) to the anti-CH2 protons f and k. The chemical shifts of butadiene protons agree well with those previously reported for the complex Os(q4-C4H6)(C0)3.25In addition, it should be mentioned that the values of Jfg= 2.6, Jjk = 3.6, Jik = Jij = 6.8, and J h f = &g = 6.7 Hz are similar t o those of 5, suggesting that there is also a significant contribution of the resonance form I1 t o the structure of 7. In the 13C{lH} NMR spectrum the carbon atoms of the diolefin give rise t o four doublet of doublets. The carbon atoms of the carbon-carbon bond disposed trans to the triisopropylphosphine ligand appear at 76.68 (CH;Jp-c = 3.9 and 1.0 Hz) and 24.40 (CH2; JP-c= 28.7 and 5.7 Hz), while the carbon atoms of the carbon-carbon bond disposed trans to the carbonyl group appear at 71.01 (CH; both Jp-c = 2.4 Hz) and 23.11 (CH2; both JP-c= 3.2 Hz) ppm. The values of etrans-p = 1.52 and Qtrans-CO = 1.4026 agree well with that previously reported for O S ( ~ ~ - C ~ H ~ ) (e ( C=O1.60).27 )~ The 31P{1H}NMR spectrum shows two doublets a t 18.9 and 6.2 ppm, with a P-P coupling constant of 9.5 Hz. The reactions of the chloro-styryl (3)and chlorovinyl (6) complexes with CH2=CHMgBr most probably involve the replacement of the C1- anion by the vinyl group to give styryl-vinyl(8) or bis(viny1)(9) intermediates that by reductive carbon-carbon coupling yield the butadiene derivatives 5 and 7 respectively (eq 5). (25)Zobl-Ruh, S.;von Philipsborn, W . Helu. Chim. Acta 1980,63, 773. (26)e = A~CI/ASCZ, where A6C = Bc,,,~ - 6cf,..
2n 1
(27)Jolly, P. W.;Mynott, R. Adu. Organomet. Chem. 1981,19,257.
4828 Organometallics, Vol. 14, No. 10, 1995
I 8
Bohanna et al.
I
1
I
I
1
1
I
I
7
6
5
4
3
2
1
0
Ppm
Figure 2. 'H NMR spectrum of complex OS(~~-C~H~P~)(CO)(P~P~~)~ (6) in CsD6 at 20 "C. rutheniwn(I1)complex Ru{(E>CH-CHPh}Cl(COXPiF'r& (4) reacts with CHz'CHMgBr to give the styryl-vinyl intermediate Ru{(E)-CH=CHph}(CH=CHzXCO)(Pipr3)z (101,which leads to the n4phenyl)butadiene Ru(q4-C&5Ph)(CO)(PiPrdz (11) (eq 6),after 15 h stirring in hexane at 50 "C.
&.
4 0
, ; 2
11
:.$
4
ppm 1
I
I
I
ppm
4
2
0
Figure 3. lH COSY NMR of the complex Os(y4-C4&)(CO)(PiPr& (7) in CDC13 at 20 "C.
R = Ph(8), H(9)
Attempts to detect these intermediates have been unsuccessful. However, in favor of this mechanistic proposal, we have observed that the chloro-styryl-
Complex 10 was isolated as red crystals in 72% yield and characterized by 'H, 13C{lH}, and 31P{1H} NMR spectroscopies. In the lH NMR spectrum, the most noticeable signals are the resonances due to the styryl and vinyl ligands. The protons of the styryl ligand give rise to two doublet of triplets a t 8.78 and 6.88ppm. The trans stereochemistry at the carbon-carbon double bond is strongly supported by the proton-proton coupling constant of 17.4 Hz which is a typical value for this arrangement.28 "he protons of the vinyl ligand display a doublet of doublets a t 7.99 ppm and two doublet of triplets a t 5.80 and 5.45 ppm. In the l3C{lH) NMR spectrum the a-carbon atom of the styryl ligand appears at 165.83ppm as a triplet with a P-C coupling constant of 13.7Hz and the /3-carbon atom a t 141.78 ppm, also as a triplet, with a P-C coupling constant of 2.4 Hz. The a-carbon atom of the vinyl ligand gives rise to a triplet at 172.65ppm with a P-C coupling constant of (28) Esteruelas, M. A,; Garcia, M. P.; Martin, M.; Niirnberg, 0.;Oro, L. A.; Werner, H. J. Orgunomet. Chem. 1994, 466, 249.
Organometallics, Vol. 14,No. 10, 1995 4829
Butadiene-Os(0) and -Ru(O) Complexes
14.6 Hz, while the fi-carbon atom appears as a broad singlet a t 135.51 ppm. The 31P{1H} NMR spectrum shows a singlet a t 39.5 ppm. Complex 11 was isolated as a yellow solid in 75% yield and characterized by elemental analysis and IR and lH, 13C{lH}, and 31P{1H} NMR spectroscopies. As for complex 5, the lH spectrum in benzene-d6 shows five signals for the diene protons at 5.30,5.20, 1.90, 1.40, and 0.07 ppm. The resonances at low field (5.30and 5.20 ppm) were assigned to the internal protons, the resonance a t 1.90 ppm was assigned t o the syn-CH2 proton, and the resonances a t 1.40and 0.07ppm were assigned to the anti-terminal protons. The H-H coupling constants are similar to those observed for 5 and therefore are consistent for a significant contribution of the metallacycle resonance form t o the structure of 11. The carbon atoms of the diene in the 13C{lH}NMR spectrum display two virtual triplets at 79.76 (Jp-c = 2.9 Hz) and 29.93(Jp-c = 3.4Hz) ppm, a double doublet at 52.03 (JP-c = 27.9 and 3.8 Hz) ppm, and a doublet at 78.62 (Jp-c = 2.9Hz). The signals at 79.76and 52.03 ppm were assigned t o the carbon atoms disposed trans to the triisopropylphosphine ligand, while the resonances a t 78.62 and 29.93 ppm were assigned to the carbon atoms disposed trans to the carbonyl group. The 31P{lH} NMR spectrum contains two broad singlets at 53.9 and 48.0ppm. The coordination number 6 for 10 can be achieved by reaction with carbon monoxide. By passage of a slow stream of this gas through a hexane suspension of 10, the dicarbonyl complex Ru{ (E)-CH=CHPh}(CH=CH2)(CO)2(PiPr3)2(12)is obtained as a white solid in 90% yield. Complex 12 can be also prepared by reaction of Ru((E)-CH=CHPh}Cl(CO)z(PiPr3)2(13)with CHF-CHMgBr (eq 7) in 82% yield.
iPr3P I
13
12
10
In agreement with the cis disposition of the two carbonyl ligands of 12, the IR spectrum of this compound in Nujol shows two v(C0) absorptions at 1990 and 1935 cm-l, and the l3C{IH} NMR spectrum in benzene& shows two triplets at 204.00and 203.96ppm with P-C coupling constants of 9.6 and 10.6 Hz, respectively. Furthermore, the spectrum contains four triplets due to carbon atoms of the styryl and vinyl and 141.41ppm with ligands a t 167.80,161.90,142.42, P-C coupling constants of 14.3,15.2,2.3,and 4.6 Hz, respectively. In the lH NMR spectrum the protons of the styryl ligand give rise to two double triplets at 8.29 and 7.09 ppm with a H-H coupling constant of 18.4Hz and P-H coupling constants of 2.5 and 2.2 Hz, while the protons of the vinyl ligand display three resonances at 7.91,6.60,and 6.03 ppm. The 31P{1H} NMR spectrum shows a singlet at 36.2ppm. In contrast to the behavior of 10, reductive carboncarbon coupling between the styryl and vinyl fragments of the saturated complex 12 is not observed, suggesting that the unsaturated ligand environment around of the
metallic center is a determinant factor for the coupling. This is in good agreement with that previously observed for the coordinatively saturated platinum(IV) complex Pt(CH&J(dppe) (dppe = bis(l,2-diphenylphosphino)ethane), where the dissociation of the I- anion is necessary for the reductive elimination of ethane.15hIn our case a bulky phosphine as triisopropylphosphine favors the formation of unsaturated five-coordinate species and therefore, most probably, the coupling process.
Concluding Remarks The reactions of the complexes M{ (E)-CH=CHR}Cl(cO)(Pih3)2 (M = OS, R = Ph, H; M = Ru, R = Ph) with CHZ'CHMgBr lead to the corresponding n-butadiene complexes M(v4-C&R)(CO)(PiPr3)2. These transformations involve the replacement of the C1- anion by the vinyl group to give styryl-vinyl or bidvinyl) intermediates that by reductive carbon-carbon coupling afford the butadiene derivatives. Reductive carbon-carbon coupling between the alkenyl fragments of the saturated compound Ru{(E)CH=CHR}(CH=CH2)(C0)2(PiPr3)2is not observed. This seems to suggest that the presence of a coordination vacancy in the starting compound could be a determinant factor for this type of coupling.
Experimental Section General Considerations. All reactions were carried out with rigorous exclusion of air by using Schlenk-tube techniques. Solvents were dried by known procedures and distilled under argon prior to use. Os{ (E)-CH=CHPh}Cl(CO)(PiPr3)2 (3),Ru{(E)-CH==CHPh}C1(CO)(PiPr~)~ (41, Os(CH=CH,)Cl(12), (CO)(PiPr& (6),and Ru{(E)-CH=CHPh}Cl(C0)2(PiPr3)2 were prepared by published methods.2 Physical Measurements. Infrared spectra were recorded as Nujol mulls on polyethylene sheets using a Perkin-Elmer 883 or a Nicolet 550 spectrometer. NMR spectra were recorded on a Varian Unity 300 or on a Bruker 300 AXR. 'H and 13C{IH} chemical shifts were measured relative to partially deuterated solvent peaks but are reported relative to tetramethylsilane. 31P{1H}chemical shifts are reported relative to H,PO( (85%). Coupling constants J and N (N = J(HP) + J ( H P ) for IH, and N = J(CP) + J ( C P ) for 13C) are given in hertz. C, H, and N analyses were carried out in a PerkinElmer 2400 CHNS/O analyzer. Preparation of Os(t14-C~~Ph)(CO)(PiPrs)z (5). A sus(3)(100 mg, 0.15 pension of O~{(E)-CH=CHP~}C~(CO)(P~P~~Z mmol) in 5 mL of toluene was treated with 0.20 mL of CH2=CHMgBr (1.0 M solution in THF) and stirred during ca. 5 min at room temperature. The resulting suspension was filtered through kieselguhr, and the solvent was removed. Addition of methanol lead to the precipitation of a white solid. The solution was decanted, and the solid was washed with methanol and dried in vacuo. Yield: 85.3 mg (85%). Anal. Calcd for CzgH5200sPz: C, 52.08; H, 7.84. Found: C, 51.94; H, 7.53. IR (Nujol, cm-I): 4CO) 1867 (SI. IH NMR (CsDs, 20 "C, labeling scheme in Figure 2): 6 7.40 (d, JH-H = 7.5 Hz, 2H, Hodho-ph), 7.21 (t,JH-H = 7.5 Hz, 2H, Hmeta.ph),7.01 (t,JH-H = 7.5 Hz, l H , Hpara.ph),5.16 (m, l H , Hd), 5.03 (m, 1H, Hc),2.36 (m, 3H, PCH(CH3)2),2.20 (m, 3H, PCH(CHdz), 1.94 (m, JH~-H, = 6.9 Hz, JH~-H, = J ~ ~ - p=b 3.9 Hz, JH~-P. = lHz, lH, Hb), = 7.2 Hz, 9H, 1.32 (m, lH, He),1.16 (dd, J H - p = 12.3 Hz, JH-H = 7.2 Hz, 9H, PCH(CH&), 1.12 (dd, J H - p = 12.6 Hz, JH-H = 6.9 Hz, 9H, PCH(CH&, 1.00 (dd, J H - p = 12.9 Hz, JH-H PCH(CH&), 0.99 (dd, J H - p = 12.0 Hz, JH-H = 6.9 Hz, 9H, PCH(CH&), -0.22 (m, JH,-H, = 6.9 HZ, JHa-Hb = JH~-P, = J~.-pb = 3.9 Hz, lH, Ha). 13C{'H} NMR (CsDs, 20 "C): 6 192.42 (dd,
4830 Organometallics, Vol. 14, No. 10, 1995
Bohanna et al.
precipitation of a yellow solid which was washed several times Jc-p = 11.5 Hz, Jc-p = 2.8 Hz, CO), 147.21 (d, Jc-p = 2.3 Hz, with MeOH and dried in vacuo. Yield: 161 mg (75%). Anal. Clpso.Ph),128.43 (d, Jc-p = 0.9 Hz, Cortho-Ph),126.36 (d, Jc-p = 1.9 HZ, Cmeta-Ph), 123.50 (d, JC-P = 1.0 HZ, Cpara-Ph), 75.48 Calcd for CzsH5zOPzRu: C, 60.08; H, 9.04. Found: C, 59.48; (dd, Jc-p = 3.7 Hz, Jc-p = 2.3 Hz, CH24HCH-CHPh), 71.98 H, 8.32. IR (Nujol, cm-'): v(C0) 1887 (9). 'H NMR (C&, 20 (dd, Jc-p = 3.7 Hz, Jc-p = 0.9 Hz, CHz=CHCH=CHPh), 44.80 = 7.5 Hz, "C, labeling scheme in Figure 2): 6 7.40 (d, JH-H 31.68 (dd, Jc-p = 26.7 Hz, Jc-p = 4.6 Hz, CH~PCHCH-CHP~), = 7.5 Hz, 2H, Hmetaw),7.01 (t,JH-H 2H, Hortho-ph),7.21 (t, JH-H (d, Jc-p = 22.6 Hz, PCH(CH&), 30.25 (d, Jc-p = 19.8 Hz, = 7.5 Hz, lH, Hpara.ph),5.30 (dd, JH.,-H, = 7.4 Hz, JH.,-H, = 4.6 PCH(CH&), 21.22 (dd, Jc-p = 5.6 Hz, Jc-p = 3.2 Hz, = J~,-pb= 7.9 Hz, JH,-H~ = 7.0 Hz, l H , Hd), 5.20 (m, JH,-H. CH2=CHCH=CHPh), 20.64 (s, PCH(CH3)2), 20.32 (9, PCH~ 4.6 Hz, lH, Hc), 2.27 (m, 3H, PCH(CH&, 2.04 Hz, J K - H = ( C H 3 ) 2 ) , 19.87 (s,PCH(CH3)z). 31P{1H}NMR (CsDs, 20 "C): 6 (m, 3H, PCH(CH3)z), 1.90 (m, JH~-H, = 7.0 Hz, J H ~ = 4.1 - ~ 13.8 (d, J p - p = 10.7 Hz), 3.2 (d, J p - p = 10.7 Hz). Hz, J H ~=-2.6 HHz, ~ J H ~=-0.2 H Hz, ~ lH, Hb), 1.40 (m, JH.-H., = 7.4 Hz, &-pa = Jh-pb = 6.3 Hz, lH, He),1.10 (m, 36H, PCHPreparation of Os(q4-CSIe)(CO)(PiPrs)a (7). A suspen(CH3)2),0.07 (m, JH.-H, = 7.9 Hz, JH~-P. = 7.8 Hz, JH,-~,, = 4.9 sion of Os(CH=CHz)Cl(CO)(PiP3)2(6)(100 mg, 0.18 mmol) in 5 mL of toluene was treated with 0.24 mL of CHz=CHMgBr Hz, JH.-H~ = 2.6 Hz, l H , Ha). 13C{'H} NMR (C&, 20" C): 6 (1.0 M solution in THF) and stirred during ca. 5 min at room 210.78 (dd, Jc-p = 15.8 Hz, Jc-p = 7.5 Hz, CO), 146.48 (d, temperature. The resulting suspension was filtered through Jc-p = 3.0 HZ, Cipso-ph),128.40 (9, Cortho-Ph),126.45 (d, Jc-p = kieselguhr, and the solvent was removed. Addition of metha1.5 Hz, Cmeta.ph),123.60 (s, cpara.ph), 79.76 (vt, Jc-p = 2.9 Hz, nol caused the precipitation of a white solid. The solution was CH~PCHCH-CHP~),78.62 (d, Jc-p = 2.9 Hz, C H 2 4 H C decanted, and the solid was washed with methanol and dried H-CHPh), 52.03 (dd, Jc-p = 27.9 Hz, Jc-p = 3.8 Hz, in vacuo. Yield: 85.4 mg (80%). Anal. Calcd for CaH48CH2-CHCH-CHPh), 30.48 (d, Jc-p = 13.0 Hz, PCH(CH&), OOSPZ:C,46.60;H,8.16. Found: C,46.71;H, 8.35. IR(Nujo1, 29.93 (vt, Jc-p = 3.4 Hz, CH2=CHCH=CHPh), 29.08 (d, Jc-p cm-'1: 4CO) 1870 (SI. 'H NMR (CDC13,20 "C, labeling scheme = 14.1 Hz, PCH(CH&), 20.45 (d, Jc-p = 15.4 Hz, PCH(CH&), in Figure 3): 6 5.05 (m, JH,-H, = JH,-Hk = 6.8 HZ, JH,-Hh = 3.9 19.89 (d, Jc-p = 14.8 Hz, PCH(CH3)z). 31P{1H}NMR (CsDs, Hz, &-pa = 3.7 Hz, J H , - ~ = 3.2 Hz, lH, HA, 4.56 (m, J H ~=- H ~20 "C): 6 53.9 (s), 48.0 ( 8 ) . JH~-H, = 6.7 Hz, JH~-H, = 3.9 Hz, JH~-P, 1Hz, lH, Hh), 2.38 Preparation of RU{(E)-CH=CHP~)(CH-CH~)(CO)~(m, 3H, PCH(CH3)2), 2.25 (m, 3H, PCH(CH&), 1.71 (ddd, (PiPr& (12). Route a. A slow stream of carbon monoxide J H ~=- H 6.7 ~ Hz, J H ~=- 2.6 H~ Hz, JH~-PL, = 3.2 Hz, lH, Hg), was bubbled for 5 min through a solution of Ru{(E)= 6.8 Hz, JH,-H~ = 3.6 Hz, J~]-pb = 2.9 Hz, J + p , 1.64 (m, JH,-H~ CH=-CHPh}(CH==CH,)(CO)(PiPr3)2 (10)(170 mg, 0.29 mmol) = lHz, lH, HJ, 1.25 (dd, JH-P = 12.9 Hz, JH-H = 7.2 Hz, 18H, in 8 mL of hexane. The deep purple solution becomes colorless = 7.5 Hz, 18H, PCH(CH3)z), 1.16 (dd, J H - p = 11.3 Hz, JH-H instantaneously. ARer concentration to ca. 2 mL white crystals = 3.5 HZ, JH,-P~ were obtained. The product was washed several times with PCH(CH3)z),-0.77 (m, J H r H h = 6.7 HZ, = 3.2 Hz, J H ~=H 2.6, Hz, lH, Hf), -1.07 (m, JH~-H, = 6.8 Hz, hexane and dried in vacuo. Yield: 160 mg (90%). = 3.6 Hz, l H , Hk). 13C{'H} NMR JH~-H] = JH~-P, = Route b. A suspension of Ru{(E)-CH=CHPh}Cl(CO)2(CDC13, 20 "C): 6 191.25 (dd, Jc-p = 11.1Hz, Jc-p = 2.5 Hz, (PiPr& (13)(180.0 mg, 0.29 mmol) in 10 mL of hexane was CO), 76.68 (dd, JC-P = 3.9 Hz, J c - p = 1.0 Hz, CH2=CHwith 0.38 mL of CHz=CHMgBr (1.0 M solution in THF) , CH=CHz), 71.01 (vt, Jc-P = Jc-p = 2.4 Hz, C H ~ ~ C H ~ H Z )treated and stirred during ca. 30 min a t room temperature. The 30.19 (d, Jc-p = 22.9 Hz, PCH(CH&), 29.11 (d, Jc-p = 19.8 resulting suspension was dried, and the residue was treated Hz, PCH(CH&), 24.40 (dd, Jc-p = 28.7 Hz, Jc-p = 5.7 Hz, with 7 mL of toluene and filtered through kieselguhr. The CH2=CHCH=CH2), 23.11 (vt, Jc-p = Jc-p = 3.2 Hz, obtained solution was dried and treated with hexane to give a C H Z ~ H C H - C H 21.11 ~ , (s,PCH(CH&), 20.81 (d, Jc-p = 1.5 white solid which was decanted and washed with hexane. Hz, PCH(CH&), 19.78 (d, Jc-p = 2.8 Hz, PCH(CH3)2), 19.74 Yield: 144 mg (82%). (s,PCH(CH3)z). 31P{1H}NMR (CDCl3, 20 "C): 6 18.9 (d, J p - p Anal. Calcd for C ~ O H ~ Z O ~ PC, ~R 59.29; U : H, 8.62. Found: = 9.5 Hz), 6.2 (d, J p - p = 9.5 Hz). C, 58.93; H, 8.31. IR (Nujol, cm-'1: v(C0) 1990 (s), 1935 (s). Preparation of Ru{ (E)-CH=CHPh}(CH=CH2)(CO)'H NMR (&De, 20 "C): 6 8.29 (dt, JH-H = 18.4 Hz, J H - p = 2.5 (Pi&& (10). A suspension of Ru{ (E)-CH-CHPh}Cl(CO)= 19.5 Hz, JH-H = 12.4 Hz, lH, RuCH=CHPh), 7.91 (ddt, JH-H (PiPrdz (4) (201.5 mg, 0.34 mmol) in 10 mL of hexane was = 2.0 Hz,lH, RuCH-CHz), 7.50 (d, JH-H = 7.6 Hz, Hz, JH-P treated with 0.44 mL of CHZ=CHMgBr (1.0 M solution in THF) 2H, Hortho-ph), 7.28 (t, JH-H = 7.6 HZ, 2H, Hmeta-ph), 7.09 (dt, and stirred during ca. 10 min at room temperature. The JH-H = 18.4 Hz, JH-P = 2.2 Hz, lH, RuCH=CHPh), 7.01 (t, resulting suspension was filtered through kieselguhr, and the JH-H = 7.6 Hz, lH, Hpara-ph), 6.60 (ddt, JH-H = 12.4 Hz, JH-H obtained orange solution concentrated to ca. 2 mL and cooled = 3.0 Hz, J H - p = 3.0 Hz, lH, RuCH-CH~), 6.03 (ddt, JH-H = at -78 "C. The red crystals obtained were decanted and 19.5 Hz, JH-H = 3.0 Hz, JH-P = 2.0 Hz, lH, RuCH-CH~), 2.43 washed with cool hexane. Yield: 142 mg (72%). 'H NMR (m, 6H, PCH(CH&), 1.07 (dvt, N = 12.9 Hz, JH-H = 6.0 Hz, (CsD6, 20 "c): 6 8.78 (dt, JH-H = 17.4 Hz, J H - p = 2.1 Hz, lH, 36H, PCH(CH&). 13C{'H} NMR (C& 20 "C): 6 204.00 (t, RuCH=CHPh), 7.99 (dd, JH-H= 15.6 Hz, JH-H = 8.7 Hz, lH, RuCH=CHd, 7.51 (d, JH-H= 7.8 Hz, 2H, Hortho-ph),7.29 (dd, Jc-p 9.6 Hz, CO), 203.96 (t, Jc-p = 10.6 Hz, CO), 167.80 (t, Jc-p = 14.3 Hz, RuCH=CH~),161.90 (t, Jc-p = 15.2 Hz, JH-H= 7.8 HZ, JH-H = 6.6 HZ, 2H, &eta-Ph), 6.98 (t, JH-H = RuCH=CHPh), 142.42 (t, Jc-p = 2.3 Hz, RuCH=CHPh), 6.6 Hz, l H , Hpara-Ph),6.88 (dt, JH-H = 17.4 Hz, J H - p = 2.4 Hz, l H , RuCH-CHPh), 5.80 (dt, JH-H = 8.7 Hz, J H - p = 3.0 Hz, 141.41 (t, Jc-p = 4.6 Hz,RuCH-CHz), 128.91 (9, Cortho-ph), lH, RuCH=CHd, 5.45 (dt, JH-H = 15.6 Hz, J H - p = 1.8 Hz, 124.90 (5, Cpara.ph)124.70 (S, Cmeta.ph),26.06 (Vt, N = 24.2 HZ, lH, RuCH=CHd, 2.44 (m, 6H, PCH(CH&), 1.08 (dvt, N = 12.9 PCH(CH3)z),19.57 (9, PCH(CH&), 19.60 (9, PCH(CH3)z). 31PHz, JH-H = 6.0 Hz, 36H, PCH(CH3)z). 13C{1H)NMR (CsDs, {lH} NMR (CsDs, 20 "C): 6 36.2 (5). 20 "C): 6 205.65 (t, J H - p = 11.3 Hz, CO), 172.65 (t, Jc-p = X-ray Structure Analysis of Os(q4-C4HaPh)(CO)(PiPrs)2 14.6 Hz, RuCH=CHz), 165.83(t,Jc-p = 13.7 Hz, RuCH=CHPh), (5). Crystals suitable for an X-ray diffraction experiment were 141.78 (t, Jc-p = 2.4 Hz, RuCH%HPh), 135.51 (s,RuCH-CHz), obtained from a saturated solution of 5 in acetone at -20°C. 128.91 (s, Cortho-Ph),124.61 (s, Cmeta-Ph),124.35 (s, Cpare-Ph),25.86 Atomic coordinates and U, values are listed in Table 2. A (vt, N = 19.2 Hz, PCH(CH3)d, 19.82 (s,PCH(CH3)z). 31P{1H} summary of crystal data, intensity collection procedure, and NMR (CsDs, 20 "C) 6: 39.5 ( 8 ) . refinement is reported in Table 3. The colorless prismatic Preparation of R~(~~-c4HaPh)(CO)(PiPrs)e (11). A crystal studied was glued on a glass fiber and mounted on a solution of Ru{(E)-CH-CHP~}(CH--CHZ)(CO)(P~P~& (10) Siemens M D - 2 diffractometer. Cell constants were obtained (215 mg, 0.37 mmol) in 10 mL of hexane was left to stir for 15 from the least-squares fit of the setting angles of 63 reflections h at 50 "C. The solution was then filtered through kieselguhr in the range 20 5 28 5 50". The recorded reflections (7116) were corrected for Lorentz and polarization effects. Three and concentrated to dryness. Addition of MeOH caused the
Butadiene-040) and -Ru(O) Complexes
Organometallics, Vol. 14, No. 10,1995 4831
Table 2. Atomic Coordinates (di x 104; xlOs for Os and P Atoms) and Equivalent Isotropic Displacement Coefficients (Az x 10s; x104 for Os and P Atoms) for the Compound
OS(P'-C~HSP~)(CO)(PZ~~)Z (5) atom
xla 22888(1) 23099(8) 10229(8) 5433(2) 434(3) 1901(4) 3007(4) 2579(3) 3701(3) 5245(4) 6261(4) 5763(4) 4259(4) 3237(4) 4199(3) 4112(3) 4639(4) 4172(4) 2329(4) 39 02(4 ) 1640(5) 822(4) 781(4) -755(4) 2202(3) 3481(4) 2821(4) -557(3) -1175(4) -1867(4) 282(4) - 112(5) -1050(4)
Yfb 16019(1) 36195(7) 8202(7) 807(2) 2191(3) 2086(3) 943(3) -35(3) -1247(3) -1387(3) -2540(3) -3591(3) -3465(3) -2305(3) 1104(3) 3925(3) 3470(3) 5259(3) 3956(3) 3464(3) 5276(3) 5001(3) 5243(3) 5022(3) 8(3) -1092(3) 857(4) 1939(3) 1499(3) 2540(3) -460(3) -1312(3) -75(4)
zlc 29402(1) 22382(5) 20098(5) 1976(2) 4048(2) 4340(2) 4338(2) 4073(2) 4029(2) 3785(2) 3759(3) 3997(3) 4249(3) 4264(2) 2320(2) 2417(2) 3386(3) 2096(3) 929(2) 439(2) 467(3) 2568(2) 3559(3) 2358(3) 1068(2) 1429(3) 294(2) 1375(2) 642(3) 2041(3) 2671(2) 2109(3) 3390(3)
u,.
Equivalent isotropic U defined as one-third of the trace of the orthogonalized U" tensor. orientation and intensity standards were monitorized every 55 min of measuring time; no variation was observed. Reflections were also corrected for absorption by an semiempirical (pscan) method.29 The structure was solved by Patterson (Os atom) and conventional Fourier techniques. Refinement was carried out by full-matrix least squares with initial isotropic thermal parameters. Anisotropic thermal parameters were used in the last cycles of refinement for all non-hydrogen atoms. Hydrogen atoms were observed and included in the refinement riding on carbon atoms with a common isotropic thermal parameter. Atomic scattering factors, corrected for anomalous dispersion for Os and P, were taken from ref 30. The function minimized was Cw([F,]- [Fc])2, with the weight defined as w-l = u2[F,1 (29)North, A. C. T.; Phillips, D. C.; Mathews, F. S. Acta Crystallogr. 1968, A24,351.
Table 3. Cestal Data and Data Collection and Refinement for Os(t14-C~Ph)(CO)(PiPr~)~ (6) formula mol wt color and habit crystal size, mm crystal syst space group
Crystal Data CZSH~ZOOSP~
a,A b, A c, A
a,deg
A deg Y deg 9
v, A3 2
D (calcd),g cm-3
668.88
colorless, transparent prism 0.37 x 0.29 x 0.34
tr&linic P1 (No. 2) 9.320(1) 11.590(1) 14.749(2) 79.34(1) 82.10(1) 72.34(1) 1486.3(3) 2 1.495
Data Collection and Refinementa diffractometer 4-circle Siemens-STOE AED i(Mo Ka)A; technique 0.710 73, bisecting geometry monochromator graphite oriented p , mm-l 4.42 scan type of29 28 range, deg 3 d 28 d 50 temp (K) 200 no. of data collecd 7116 no. of unique data 6779 (Ri,t = 0.025) unique obsd data 6357 (F,2 4.00(F0)) 300 no. of params refined R, Rw 0.0230,0.0245 a R = (Z[IFol - 1FcIl)EFo; Rw = (Z([IFol - l F c l l ) ~ 1 ' 2 ) ~ ( l F o l ~ 1 ' 2 ) , w-l = u2(Fo) 0.000292(F0)2.
+
+ 0.000292[FO2].Final R
and Rw values were 0.0230 and 0.0245. All calculations were performed by the use of the SHELXTL-PLUS system of computer program.31
Acknowledgment. We thank the DGICYT (Project PB 92-0092, Programa de F'romocidn General del Conocimiento) and EU (Project Selective Processes and Catalysis Involving Small Molecules) for financial support. E.O. thanks the Diputacidn General de Aragdn (DGA) for a grant. Supporting Information Available: Tables of anisotropic thermal parameters, atomic coordinates and U values for hydrogen atoms, experimental details of the X-ray study, bond distances and angles, and selected least squares planes for 6 (12 pages). Ordering information is given on any current masthead page.
OM9503407 (30)International Tables for X-Ray Crystallography; Kynoch Press: Birmingham, England, 1974; Vol. IV. ( 3 1 ) Sheldrick, G. M. SHELXTL PLUS: Siemens Analytical X-ray Instruments, Inc.: Madison, WI, 1990.
