Organometallics 1996, 14, 1044-1052
1044
Reactions of Primary Amines with (q5-Pentadieny1)-and ( q5-Methylpentadienyl)tricarbonylmanganese Complexes. Synthesis, Characterization, and Structural Studies Ma. Angeles Paz-Sandoval,* Rosalina Sanchez Coyotzi, and No6 Zufiiga Villarreal Departamento de Quimica, Centro de Investigacibn y de Estudios Avanzados del Instituto Politkcnico Nacional, Apartado 14-740,Mkxico, D.F. 07000,Mixico
Richard D. Ernst and Atta M. Arif Department of Chemistry, University of Utah, Salt Lake City, Utah 84112 Received November 18,1994@ Reactions of primary amines with (q5-pentadieny1)tricarbonylmanganese(1)have been investigated and compared with analogous secondary amine and phosphine reactions. Cyclohexylamine reacts with 1 to give the isomeric complexes [l-(cyclohexylamino)-(2-4q3)-pentenylltricarbonylmanganese,Mn[NH(C6H11)(CH2-q3-CHCHCHCH3)1(C0)3 (2)and the l-(cyclohexy1amino)-(1-3-q3)-pentenyl complex Mn[NH(C6Hd (q3-CHCHCHCH2CHd1(C0)g (4). In both cases, nitrogen is added regioselectively to the terminal carbon atom on the pentadienyl ligand and also becomes coordinated to the manganese atom. In the case of the isopropyl- and tert-butylamines, the reactions with complex 1 form exclusively [l-amino(1-3-q3)-pentenylltricarbonylmanganese complexes Mn[NH(R) (q3-CHCHCHCH2CH3)1(C0)3 (R = X3H7 ( 5 ) )t-CdHg (6)), while mixtures of Mn[NH(R) (q3-CHCHCHCH2CH2CH3)1(C0)3 (R = i-C3H7 (ll),t-C4H9 (12))and Mn[NH(R) (q3-C(CH3)CHCHCH2CH3)1(C0)3 (R = i-C3H7 (1l’),t-C4Hg (12’))regioisomers are obtained from the reaction with (q5-methylpentadieny1)tricarbonylmanganese (lo),except for the case of R = cyclohexyl,from which the l-cyclohexyl(l-3)-q3)-hexenyl complex 13 is obtained. The conversion from ll’, 1 2 to 11,12,respectively, suggests that 11’ and 1 2 are the kinetic and 11 and 12 the thermodynamic products in these reactions. Compound 2 represents a formal 1,5-addition product to the pentadienyl ligand and is structurally novel for the amine addition compounds. Its X-ray crystal analysis revealed that the cyclohexylamine group has coupled to the pentadienyl group, leading to a l-cyclohexylamino-(2-4-q3)-pentenyl fragment coordinated through the nitrogen atom and the allyl moiety to the manganese atom. This structure is similar to that for the phosphorus analog 3. The crystals of 2 are orthorhombic, space group P212121, with cell dimensions of a = 7.449(5) A, b = 12.572(2)A, c = 16.350(3)A, and V = 1531.15 A3 (2= 4). The structure was refined to discrepancy indices of R = 0.0402 and R, = 0.0460 for 1046 reflections having I > 30(I). From differences in bond lengths and angles it appears that the strain induced by coordination of the enyl-amine ligand is much lower than that resulting for the analogous enyl-phosphine complex 3. Single-crystal X-ray diffraction studies of 5 and 6 show that their aminopentenyl ligands are bonded to manganese through an r3 interaction and also by nitrogen coordination. Com ound 5 crystallizes in the monoclinic space group P21/c, with a = 10.308(3) A, b = 10.935(2$, c = 12.359(2) A, ,8 = 110.56(2)”,and V = 1304.39 Hi3 (2 = 4); R = 0.0306 and R, = 0.0324 for 1614 reflections with I > 341). Crystals of 6 are orthorhombic space group Pbca with a = 7.197(1) A, b = 18.879(2)A, c = 20.561(3) A, and V = 2793.83 (2= 8);R = 0.0524 and R, = 0.0569 for 1037 reflections with I > 30(I). The two complexes have distorted-octahedral geometries without significant differences relative t o analogous secondary amine derivatives. Complexes 4-6 and 11-13 proved to be more reactive species than the corresponding aminopentenyl derivatives derived from secondary amines.
i3
Introduction Investigations into the reactivity of the neutral (r5pentadienylltricarbonylmanganese complex with organolithium compounds,l dienes,2secondary amines; and tertia# and secondary phosphines5 have been previAbstract published in Advance ACS Abstracts, January 15,1995. (1)(a) Roell, B. C., Jr.; McDaniel, K. J.A m . Chem. SOC.1990,112, 9004. (b) Roell, B.C., Jr.; McDaniel, K.; Vaughan, W. S.; Macy, T. S. Organometallics 1993,12,224. (2)Kreiter, C.G.;Lehr, K.; Heeb, G. Z. Naturforsch. 1991,46B,941. @
ously reported. This complex was found to exhibit significant differences in its reactions with nucleophiles, and (r5as compared to related (~5-cyclohexadienyl)-1b!6 ~ycloheptadienyl)Mn(C0)3~ species. Furthermore, in (3) Zufiiga Villarreal, N.; Paz-Sandoval, M. A,; Joseph-Nathan, P.; Esquivel, R. 0. Organometallics 1991,10,2616. (4)Paz-Sandoval, M.A,; Powell, P.; Drew, M. G. B.; Perutz, R. N. Organometallics 1984,3, 1026. (5)Paz-Sandoval, M. A,; Juarez Saavedra, P.; Zdiiiga Villarreal, N.; Rosales Hoz, M. J.; Joseph-Nathan, P.; Emst, R. D.; Arif, A. M. Organometallics 1992,11, 2467.
0276-733319512314-1044$09.00/0 0 1995 American Chemical Society
Organometallics, Vol. 14,No. 2, 1995 1045
Reactions of Amines with Pentadienyl-Mn(CO)s
Scheme 1 C6H5
\
-'S
I
I
2
4
C6HS
f
t X'
I
Mn(CO)3
1
Primary Amines
R(
'Rz
Primary Amines 2 X=N R,=H
8 X=N Rl+R2=(CH2)5 RZ=C~H~~
Secondary Phosphine
Secondary Phosphine 9
these reactions a strong dependence of the pathway upon the nature of the nucleophile utilized was clearly osberved. For cases in which the nucleophiles contained heteroatoms, the heteroatom generally became attached t o both the dienyl fragment and the metal center. Notably, in earlier studies involving related acyclic ligands and heteroatom-containing nucleophiles, the heteroatom similarly became attached to both the products containing an organic acylic ligand and the metal enter.^?^ Other approaches have also led t o related acyclic Jc-ligands incorporating heteroatoms. Various (y5-l-azapentadieny1)Mn(C0)3complexes have been prepared from the corresponding 1-oxopentadienyl derivatives,1° and recently some amine-substituted (y4oxopentadieny1)tricarbonylmanganesecomplexes, which have also been described as (y4-allyl-amide)Mn(CO)3, have been synthesized from the reaction of an (vlpentadienoyl)Mn(C0)5 complex with selected amines (6)(a)Padda, R. S.; Sheridan, J. B.; Chafee, K. J.Chem. Soc., Chem. Commun. 1990,1226. (b) Sheridan, J. B.; Padda, R. S.; Chafee, K.; Wang, C.; Huang, Y. J. Chem. Soc., Dalton Trans. 1992,1539. (7)Wang, C.; Lang, M. G.; Sheridan, J. B.; Rheingold, A. L. J . Am. Chem. Soc. 1990,112,3236. (8) (a)Melhdez, E.; Arif, A. M.; Ziegler, M. L.; Ernst, R. D. Angew. Chem., Int. Ed. Engl. 1988,27, 1099. (b) Kirillova, N.I.; Gusev, A. L.; Pasynskii, A. A.; Struchkov, Y. T. J. Organomet. Chem. 1973,63, 311. (c)Abel, E. W.; Rowley, R. J.;Mason, R.; Thomas, K. M. J. Chem. SOC.,Chem. Commun. 1974,72. (d) King, R.B.; Hodges, K. C. J.Am. Chem. Soc. 1976,97,2702. (9)Alper, H.; Paik, H.-N. J. Organomet. Chem. 1976,122, C31. (10)Cheng, M.-H.; Cheng, C.-Y.; Wang, S.-L.; Peng, S.-M.; Liu, R.S. Organometallics 1990,9,1853.
X=P
RI=R~=C~H~
and in the presence of an amine N-oxide.ll Also, some pseudo-(a-aminoally1)cobaltcomplexes Co(COh{RCHCHCHNHR'} have been prepared from the reaction of monoaza dienes with Coz(C0)~ under a H2 atmosphere.12 It was earlier demonstrated in these laboratories that C5H7Mn(C0)3(1) reacted with secondary amines3 and diphenylphosphine5 to yield (aminopenteny1)-or (phosphinopenteny1Nricarbonylmanganesecomplexes, respectively, as shown in Scheme 1. The first step in both reactions could involve addition of the nucleophilic nitrogen or phosphorus atom to a terminal carbon atom of the pentadienyl ligand in a regioselective manner. These reactions have led t o a variety of new isomeric complexes having aminopentenyl or phosphinopentenyl ligands bonded to a manganese center through the heteroatom and y3-allyliccoordination involving various segments of the pentenyl chain. While secondary amines exclusively afford (1-amino-(1-3-y3)-pentenyl)tricarbonylmanganese complexes, such as 7 and 8, diphenylphosphinegives isomeric [l-(diphenylphosphin0)(2-4-q3)-pentenyl]tricarbonylmanganese(3)and [l-(dipheny1phosphino)-(3 -5-y3)-pentenyl]tricarbonylmanganese (9) species (Scheme 1). The fact that neither the phosphine nor the amines produce all three possible isomers from the addition to the pentadienyl ligand (ll)AbuBaker, A.; Bryan, C. D.; Cordes, A. W.; Allison, N. T. Organometallics 1994,13,3375. (12)Beers, 0.C. P.; Elsevier, C. J.; Ernsting, J.-M.; De Ridder, D. J. A.; Stam, C. H. Organometallics 1992,11, 3886.
1046 Organometallics, Vol. 14, No. 2, 1995
prompted us to examine the reactivity patterns for C5H7Mn(C0)3 with primary amines, for which it should be expected that the NH function would remain in the synthesized species. The characterization of the new isomers derived from the nucleophilic addition of primary amines, as well as their reactivity and comparison with analogous species previously r e p ~ r t e d ,form ~ , ~ the basis of this paper.
Experimental Section All operations were carried out under an atmosphere of dinitrogen with standard Schlenk-line techniques. Solvents were purified by conventional methods and distilled under dinitrogen prior t o use. The starting materials l4and 104J3 were prepared by published methods. NMR spectra were obtained with a JEOL GSX-270 spectrometer, IR spectra on a Nicolet MX-1-FT spectrophotometer, and mass spectra on a Finnigan MAT 95 instrument. Elemental analyses were performed by Oneida Research Services Inc., Whitesboro, NY. Reaction of CsH&Mn(CO)3 (R = H (l),CH3 (10)) with Primary Amines (H2NR; R = C a l l , C3H7, C4Hs). Unless otherwise described below, in a typical synthesis the appropriate dry, freshly purified amine was syringed into a Schlenk tube containing a cyclohexane solution of 1or 10. The yellow reaction mixture was filtered into a thick-walled Pyrex ampule (6 x 2.5 cm), which was subsequently sealed under vacuum (1 x mmHg), placed in a steel container, and heated in an oil bath a t 110-115 "C for 7 h. The reaction mixture contained a white precipitate, which was filtered off and discarded, after the ampule was opened. Removal of the solvent and excess amine under reduced pressure left either a yellow solid or an oil, which was purified under nitrogen by chromatography on Florisil using different eluent mixtures of petroleum ether and diethyl ether. In both cases, a yellow band eluting first from the column with hexane was identified as unreacted 1 or 10. A second yellow band was collected using hexane-diethyl ether, which was reduced in volume t o ca. 5 mL and cooled to -5 "C, affording the new species below as yellow solids. (a) HzNR, R = C a l l (2). A 60-mL yellow cyclohexane solution of 1 (500 mg, 2.43 mmol) with cyclohexylamine (1.44 g, 14.5 mmol) was heated under reflux over 4 h, changing to a lemon color. Chromatography using petroleum ether afforded 217 mg (29.2% yield) of a mixture of isomers 2 and 4. Complex 2 (mp 115.5-116.5 "C) was obtained pure after several days by fractional sublimation under high vacuum (4 x mmHg) a t 30-40 "C, yielding lemon yellow crystals of sublimed 2, while complex 4 remained in the bottom of the ampule. Mass spectrum (17 eV; mle (relative intensity)): 55 (11, 84 (111, 153 (loo), 166 (791, 167 (lo), 221 (38), 249 (111, 277 (61, 305 (3). IR (hexane, YCO): 2006 (s), 1916 (s), 1910 (s) cm-l. (b) HzNR, R = C a l l (4). The reaction mixture of 1 (300 mg, 1.46 mmol) and cyclohexylamine (13 g, 15 mL, 130 mmol) was heated for 3 h in an ampule. Chromatography using (13) In the synthesis of (r15-ezo-CH3C~Hs)Mn(C0)3 (10)we found a mixture of two isomers (q3-C,jHg)Mn(C0)4,in which the terminal methyl groups of the substituted carbon-carbon double bond are in ex0 (loa) and endo (lob) positions, respectively. The ratio 0.5:0.3:0.2 for 10:lOa:lOb was obtained aRer refluxing the mixture of MnBr(CO)5 and CeHgSnBu3 in tetrahydrofuran for 6 h. Chromatography on netural alumina with hexane afforded a mixture of products, which possess very similar solubilities. Compounds lo3and 10a19have been characterized as described, while 10b has not been previously reported. lH NMR for 10b (270 MHz, CDC13): 6 0.8-1.15 (m, H1 endo), 1.95 (ddd, H1 exo), 4.24 (dt, H2), 3.2 (t, H3), 5.38 (m, H4), 5.18 (m, H5), 1.46 (d, CH3). 13C NMR (67.80 MHz, CDC13): 6 37.3 (Cl), 92.0 (C2), 63.4 (C3), 130.9 (C4), 123.7 (C5), 17.3 (CH3). The mixture of isomers 10a and lob is converted to 10 after prolonged reflux. The reaction of either pure 10 with amines or of the mixture of 10, l o a , and 10b with amines afforded the same tricarbonyl products, without evidence of any tetracarbonyl species.
Paz-Sandoval et al. petroleum ether-diethyl ether (6:4) afforded a pale yellow powder: mp 112-115.5 "C dec. This complex 4 is isolated pure in 45% yield (200 mg). Anal. Calcd for C14H20N03Mn: C, 55.08; H, 6.56; N, 4.59. Found: C, 54.90; H, 6.51; N, 4.17. Mass spectrum (17 eV; mle (relative intensity)): 55 (2),84 (201, 166 (loo), 167 (30), 221 (56), 249 (19), 277 (331, 305 (20). IR (hexane, Y C O ) : 2008 (s), 1924 (s), 1908 (s) cm-'. (c) HzNR, R = CsH7 (5). A 5 mL cyclohexane solution of 1 (300 mg, 1.46 mmol) and 10 mL of isopropylamine (120 mmol) were used for this reaction. The yellow compound was dissolved in the minimum volume of hexane and chromatographed twice using petroleum ether-diethyl ether in a 9:l ratio. Bright yellow crystals (mp 114-115 "C dec) were obtained in 80.3% yield (310 mg) by recrystallization from diethyl ether-hexane (1:9) after 1 week a t -15 "C. Anal. Calcd for CllH16N03Mn: C, 49.81; H, 6.03; N, 5.28. Found: C, 48.85; H, 5.83; N, 5.31. Mass spectrum (17 eV; mle (relative intensity)): 126 (loo), 181 (22), 209 (71,237 (171,265 (15). IR (hexane, YCO): 2007 (s), 1922 (s), 1907 (SI cm-'. (d) H&R, R = C4Hg (6). A 10 mL cyclohexane solution of 1 (337 mg, 1.64 mmoles) and 6.96 g (10 mL, 9.52 mmol) of tert-butylamine were heated in a sealed ampule for 6.5 h. A green powder which had formed was filtered under an inert atmosphere. Removal of the solvent and amine in vacuo afforded a golden yellow powder. Direct recrystallization from hexane gave 271 mg of golden crystals (59.2% yield). Very mmHg) slow sublimation (4 months) under vacuum (4 x at -30 "C afforded single crystals suitable for X-ray studies; mp 90-92 "C. Mass spectrum (20 eV; mle (relative intensity)): 140 (loo), 195 (32), 223 (181,251 (231,279 (13). HRMS for C12HlsN03Mn: found 279.0654 amu, calcd 279.0667. IR (cyclohexane, YCO): 2000 (s), 1920 (s), 1903 (s) cm-l. (e)H&R, R = C3H7 (11, 11'). A 5 mL cyclohexane solution of 10 (300 mg, 1.36 mmol) and 10 mL (120 mmol) of isopropylamine were used for this reaction. After chromatography with petroleum ether-diethyl ether (9:1), a mixture of isomers 11 and 11' in a ratio of 7:l was formed in 7.4% yield (28.1 mg). IR (cyclohexane, YCO): 2006 (s), 1921 (s), 1907 (s) cm-'. (0H&R, R = C4H9 (12, 1 2 ) . After the usual procedure, the reaction mixture of 10 (320 mg, 1.45 mmol) and tertbutylamine (10 mL, 95 mmol) afforded, after recrystallization with hexane, a mixture of pale yellow isomers 12 and 1 2 (9: 1)in 18.8%yield (80 mg). Anal. Calcd for C13HlsN03Mn: C, 52.90; H, 6.83; N, 4.78. Found: C, 51.95; H, 6.29; N, 4.47. Mass spectrum (mle (relative intensity)): 56 (6.61, 154 (1001, 209 (231,237 (131, 265 (171, 293 (10). IR (hexane, VCO): 2006 (s), 1922 (s), 1907 (s) em-'. (g) H m , R = C a l l (13). The reaction mixture of 10 (310 mg, 1.41 mmol) and cyclohexylamine (25 mL, 220 mmol) was heated under reflux without solvent. After chromatography with petroleum ether-diethyl ether in an 8:2 ratio an amber solid, which decomposes a t 103-106 "C without melting, was isolated in 6.6% yield (26.4 mg). Reaction of [(q5-C5H7)Mn(C0)31(1) with CeH5CHzSH. A solution of complex 1 (300 mg, 1.46 mmol) in 40 mL of cyclohexane was stirred with C G H ~ C H ~ S (1.27 H g, 1.20 mL, 10.2 mmol). Immediately, the color of the solution changed from yellow t o orange. The resulting solution was stirred a t room temperature for 5 h and then evaporated to dryness in vacuo. Sublimation of the excess benzyl mercaptan afforded a yellow, oily powder. This mixture was washed with hexane, and recrystallization of the resulting yellow powder with CH2Cl2-hexane (3:l) followed by chromatography of the oily residue on Florisil with diethyl ether-hexane (1:9) afforded 170 mg of the cubane complex14(11.1% yield). A yellow band eluting first from the column with hexane was the starting material 1, while the second yellow band collected, as described above, afforded the cubane species as orange crystals. Single-Crystal X-ray Diffraction Studies. Single crystals of the various compounds were prepared by cooling ( 5 ) or sublimation (6 and 2) as described above. For data collection, the crystals were mounted in glass capillaries under nitrogen
Reactions of Amines with Pentadienyl-Mn(CO)s
Organometallics, Vol. 14, No. 2, 1995 1047
and then transferred to an Enraf-Nonius CAD 4 rotating anode diffractometer, on which unit cell determination and data collection were carried out. No significant decomposition was observed, as the intensities of several standard reflections remained essentially constant. Direct methods, using the SDP programs, were used to locate the metal atom and most lighter atom positions, after which any remaining non-hydrogen atoms were located from a difference Fourier map. Hydrogen atom locations were determined from a Fourier map or placed in idealized positions but, unless otherwise indicated in the tables, were not refined. Other pertinent information relative to crystal data and data refinement may be found in Table 3.
Scheme 2
2 (clI
+
Mn(W
RNHZ
-
r
1 R- N-Mn(CO)3
L
k
Synthetic and Spectroscopic Results and Discussion The reaction of Mn(q5-C5H7)(C0)3(1)with an excess of a primary amine in cyclohexane leads t o the formacomtion of Mn[NH(R)(q3-CHCHCHCH2CH3)l(C0)3 plexes (5, R = i-CsH7; 6, R = t-C4H9). In the case of R = C6Hl1, however, the analogous reaction under reflux led t o a mixture of the isomers Mn[NH(CsHll)(q3CHCHCHCH2CH3)1(C0)3(4) and Mn[NH(C6H11)CH2q3-CHCHCHCH31(C0)3(2),which are yellow crystalline solids. Complex 4 can be isolated as the only product if the reaction is carried out in a vacuum-sealed ampule without solvent (Scheme 1). The main difference between the products 4-6 and 2 is that while in 4-6 the pentenyl group is bonded to the metal atom through the three nearest carbon atoms to nitrogen, 2 has its q3enyl system separated from the nitrogen atom by a single saturated carbon center (Scheme 1). Complexes 4-6 all display similar spectroscopicproperties, demonstrating that in each case the nitrogen atom has added regioselectively to the terminal carbon atom on the pentadienyl ligand and also becomes coordinated to the manganese atom. During this process a single proton abstraction from the NH2 group also occurred, leading to the formation of the neutral substituted aminopentenyl complexes in a fashion identical with that observed for related secondary amine derivat i v e ~ .The ~ reaction rates were found to be dependent on the concentration of the ligand, even t o a greater extent than found for the secondary amine s p e ~ i e s . ~ When a 1:7 ratio of 1 and isopropylamine was used, infrared spectroscopic data showed that no significant conversion to products had taken place after 7 h. In contrast, under similar conditions, the analogous aminopentenyl complexes derived from secondary amines were readily formed. In addition, the reaction after 7 h using a 1230 ratio of reactants 1 and isopropylamine showed complete consumption of 1. A similar situation also applied t o the reaction of syn-(1-methylpentadieny1)tricarbonylmanganese (10)with primary amines (vide infra). Reactions of 10 with isopropylamine or tertbutylamine in 1:86 and 1:66 ratios led t o the two different regioisomers 11, 11’and 12, 12,respectively, (14)Characterization of [Mn(C0)3(SCH2C6H5)]4: lH NMR (90MHz, CDC13) 6 3.66(s,CHz), 7.42(8,C&); 13C NMR (22.49MHz, CDC13) 6 41.4(CHz), 129 (Cp), 129.1,130.6 (Co, m), 135.1 (C,); IR (CHC13, YCO) 2017 (vs), 1942 (vs, br) cm-l; MS for C4oH28012S4Mn4 found 1047.4 0.3 amu, calcd 1048.67;mle 1048,964,788,712,620,534,530,438, 356,348,347,265,262,261,238,220, 183, 178,174,165,151,142, 123,119,110,91,87,55. Anal. Calcd for C40H28012S4M1-u: C, 45.8; H, 2.67;S, 12.21. Found: C, 45.7;H, 2.8;S, 13.12. (Buttenvorth Laboratories Ltd., Middlesex, U.K.).Atomic absorption spectrophotometry shows 19.5% Mn us 20.99% (calcd). Mp: 205 “C. A similar tetranuclear species has been reported for [Mn(C0)3(RC6H& (R = S, Se); see: Jaitner, P. J. Organomet. Chem. 1981,210,353.
*
11 R= C3H7
11’ R= C3H7
12 R= C4Hg
12’ R= C,Hg
13 R= C6Hll
11 and 12 being the thermodynamic products and 11’ and 12’the kinetic ones (Scheme 2). The regioisomers were found in ratios of 7:l and 9:l for 11, 11‘ and 12, 12’,respectively. The much smaller abundance of the kinetic isomers 11’and 1 2 compared with the secondary amine systems, which were prepared in a complex: amine ratio of 1:8 in refluxing cyclohexane,3 can be attributed to the higher concentration and stronger reaction conditions required for the synthesis of the primary amine species (see Experimental Section). In line with earlier observations utilizing either nitrogen- or carbon-based nucleophiles or hydride ion, the attack of the nucleophile on the unsymmetrically substituted pentadienyl 10 does not occur preferentially at the least hindered carbon atom3 (cf. 11’and 12). This could be consistent with an electronic effect due to the methyl group, which would lead to nucleophilic attack by amine, whether coordinated or not, on the relatively electron deficient dienyl ligand. A subsequent proton shift, presumably metal-mediated, to the terminal CH2 group would lead t o 2 as an isolable species for R2 = C6Hll (Scheme 1)or as a presumed intermediate for R2 = i G H 7 or t-CdH9. After what might be termed a /3-hydride elimination from the saturated methylene group in 2, and hydride transfer t o the methylsubstituted end of the diene ligand, one would arrive at the y4-aza diene complexes 4-8. A n alternative in the present case would be coordination of the amine, yielding an q3-dienylcomplex, analogous to known (q3C5H7)Mn(C0)3(PR3)complexes,4 followed by oxidative addition of the N-H bond to the metal center and transfer of the hydrogen atom to the (unsubstituted) end of the q3-dienyl ligand. This could ultimately lead to placement of the HNR group on a more substituted carbon center. Unfortunately, we were unable to gain NMR spectroscopic evidence for either the presumed v3dienyl complex or any manganese hydride intermediates. However, the last proposal might be more likely, since otherwise one would probably expect the electrondonating methyl group to retard nucleophilic attack at its attached carbon atom, and at best a mixture of products would be expected. Similarly, complex 13 was isolated as the exclusive product in low yield, using a
1048 Organometallics, Vol. 14,No. 2, 1995
Paz-Sandoual et al.
Table 1. *H NMR Data (6) for the Aminopentenyl Complexes" complex
Rz
H1
H2
H4
3.37 (m) 2.40 (m), 2.76 (dd, 12, 7.2), 2.83 (dd, 12, 5.3) 4 4.65(t,-8) 4.18(dd,9.2,3.3) 0.49(m) 1.75-1.96(m) 4' 5.43 (t, -8) 4.65 (dd, 9, 3.3) 1.02 (m) 1.4-2.2 (m) 5 4.54 (t, -8) 4.14 (dd, 8.8, 2.7) 0.42 (m) 1.85 (m) 6 4.90(t, 7.5) 4.26 (dd,9, 3.3) O S (m) 2.0(m) lld 4.57 (t) 4.19 (d, 7.9) 0.63 (m) 1.5-2.0 (m) 12" 4.87 (t) 4.27 (d, hr) 0.57 (m) 1.57-2.12 (m) 13d 4.64 (t, 8.2) 4.22 (dd, 9.2, 2.8) 0.6 (m) 1.45-2.0 (m) 2
1.7-2.0 (m) 4.34 (dd, 11)
H3
H5
H6
2.18, (d, 5.3) 0.7-2.0 (m) 1.2(t,7.3) 1.21 (t. 7.3) 1.18 (t, 7.3) 1.3 (t, 6.6) 0.2-2.0 (m) 0.1-2.0 (m) 0.1-2.1 (m)
H7 2.55 (m)
0.1-1.4(m) 0.15-0.35(m) 0.9-2.2 (m) 0.9-2.2 (m) 1.72-1.92 (m) 0.33 (d, 5.9) 0.7 (s) 1.86 (m) 0.33 (d, 5.3) 0.6 (s) 0.1-2.1 (m) 0.1-2.1 (m)
H8 1.1-1.3 (m)
H9-11
N-Hb
1.0-1.7(m) -2.0 (hr, 18)
1.55-1.73(m) 0.1-1.4(m) -1.3(br,22) 0.9-2.2 (m) 0.9-2.2 (m) -0.6 (br, 25) 0.51 (d, 6.6) -1.45 (br, 24) 0.7 (s) 0.7 (s) -0.95 (br, 19) 0.52 (d, 5.3) - 1.04 (br, 23) 0.6 (s) 0.6 (s) - 1.07 (br, 23) 0.1-2.1 (m) 0.1-2.1 (m) -1.23 (br, 24)
2 Hz. In CDC13. For numbering, see Scheme 1; in C6D6 relative to Me& (d 0); 270 MHz. J values are given in parentheses. Half-height width, ~ 1 1 in dFor numbering, see Scheme 2. CHdC5): d 0.96 (t, -7) (ll),0.98 (t, br) (12), 0.95 (t. 7.0) (13).
1:150 ratio of lxyclohexylamine, after 7 h of reflux. Complexes 4-6 and 11-13 proved t o be less easily handled than the corresponding aminopentenyl derivatives derived from secondary amines, in particular being much more air-sensitive. It is interesting to note that, under the reaction conditions used for the formation of the primary amine species, the aminopentenyl derivatives from secondary amines afforded instead golden yellow complexes such (R2 = (CH2)5, as Mn[r3-CH(NR2)CHCHCH2CH31(C0)4 R = MeI3as the only product. However, for the primary amine derivatives from 1 or 10 there was no evidence of any related tetracarbonyl species, even though some reactions using 10 were carried out in the presence of a mixture of tetracarbonyl isomers 10a and 10b.13 This fact probably reflects the greater steric crowding accompanying the species with -NR compared to those with -NH. Since the Mn-N bond distances for secondary vs primary amine products are not significantly different in the solid state (vide infra),there would not seem to be much difference in the inherent Mn-N bond energies. The reaction of equimolar 5 and PMezPh in cyclohexane, after 6 h at room temperature, afforded essentially only starting materials. In addition, after 4 h reaction of 1 equiv of PMezPh with 5 or 6 in refluxing cyclohexane, it was observed that the aminopentenyl complexes 5 and 6 had decomposed,instead of affording complexes such as Mn(r3-CH(NHR)CHCHCH2CH3)tCO)3PMezPh analogous to those previously obtained under similar experimental conditions for the related secondary amine addition p r o d u ~ t s .Possibly, ~ it is again the greater steric bulk of an NR us NH species which leads to the difference. Thus, if the addition of PMeaPh requires initial slippage of the amine center away from the metal, the bulkier NR (us NH) species should be the one to promote PMezPh coordination. Of course, it is also possible that the NH function may not be completely innocent in this matter and may allow for other pathways to be followed (e.g., imine formation, etc.). Further studies are in progress in order to gain a better understanding of the differences observed. A similarly attempted addition reaction of allylamine to complex 1 afforded after 7 h at 110 "C a complex mixture of products, in which the corresponding [l(allylamino)-(1-3-~3)-pentenyl]tricarbnylmanganese species was clearly detected by 13C NMR15 spectroscopy. There was no evidence of any species in which the double bond of the allyl fragment had become coordi(15) 13C NMR (67.80 MHz, C6D6): 6 75.8 (Cl), 88.2 (C2), 65.1 (C3), 27.5 (C4), 14.5 ((251, 53.3 ((261, 133.6 (C7), 118.0 (C8).
nated to the metal center. Attempts t o separate the components of the mixture were unsuccessful. It was also of interest to explore the mode of reactivity for other heteroatom species. Reaction of 1with benzyl mercaptan afforded 1,3-pentadiene along with an orange cubane complex, [Mn(C0)3SCH2C6H514,14even when a stoichiometric ratio of reactants had been used, and the reaction was carried out at room temperature (see Experimental Section). To what extent if any the difference is due to the greater acidity of the mercaptan, or to the extra lone pair present on the sulfur atom, is not clear. A detailed NMR study of complex 1 in deuterated benzene revealed formation of 1,3-pentadiene immediately after addition of the benzyl mercaptan, with consequent formation of the cubane structure. After 6 h a t 33 "C the consumption of 1 was complete. IR spectroscopic monitoring of this reaction was not helpful, due to the spectral patterns of 1 and the cubane complex being quite ~imi1ar.l~ The isolated sulfurmanganese compound was not observed to react with excess PMezPh in cyclohexane even after 3 h under refluxing conditions, evidencing the high stability of the complex. SpectroscopicData. The metal carbonyl fragments in complexes 2, 4-6, and 11-13 produce three strong vco absorption bands in the infrared region. The intensity patterns, which suggest fac arrangements, as well as the frequency values (see Experimental Section) are quite similar to those reported for the aminopentenyl complexes derived from secondary amine^.^ These results indicate that the aminopentenyl ligands from primary and secondary amines give rise to similar interactions with the manganese atom. Therefore, the IR spectra do not provide evidence supporting stronger (7 donation by the -NHR compared to an -NRz group. The IR spectrum of the phosphinopentenyl complex (3)5 shows frequency bands very similar to those of complex 2.
lH and 13C NMR data for the aminopentenyl complexes are listed in Tables 1 and 2, respectively. The similarity of the NMR spectra of 4-6 and 11-13 t o those of the aminopentenyl complexes derived from secondary amines led us to propose that all these complexes have the same pentenyl ligand conformation. The most characteristic feature in the lH NMR spectra of complexes 4-6 and 11-13 is a broad high-field signal (6 -0.95 to -1.45, C ~ D Gwith ) a v112 value of -22 Hz, attributed to the NH moiety. We were not able to obtain a 15NNMR spectrum. However, the appearance of 15N satellites in the lH NMR spectrum (observedby inverse
Organometallics, Vol. 14, No. 2, 1995 1049
Reactions of Amines with Pentadienyl -Mn(CO)J
Table 2. 13C NMR Data (6) for the Aminopentenyl Complex& R2
complex
C1
c2
c3
c4
c5
C6
c7
C8
2
67.5 75.7 75.8 (d, 193) 74.5 (d, 200) 75.8 d 73.4 d 75.5
105.1 88.3 88.3 (d, 164) 86.9 (d, 170) 88.8 88.3 86.3 87.0 88.7
48.6 63.2 63.2 (d, 152) 63.9 (d, 158) 60.8 61.1 60.5 61.3 60.8
51.8 27.5 27.4 (t, 127) 28.4 (t, 134) 36.5 27.4 36.4 27.4 36.5
20.5 17.8 17.7 (q, 126) 18.7 (9. 134) 26.7 17.9 26.7 18.3 26.8
63.2 60.4 53.7 (d, 140) 55.0 53.8 49.3 53.9 52.2 60.3
31.5 35.6 23.7 (q, 132) 30.0 (q, 134) 23.7 24.3 28.9 30.1 35.6
31.0 34.1 22.9 (q, 128) 30.0 (q, 134) 22.9 23.4 28.9 30.1 34.0
4
5
6
llb 11’‘ 126 12’c 13b
c9
c10 c11
25.4 25.3
25.0 24.6 24.9 24.7
30.0 (q, 134) 28.9 30.1 25.3
24.9 24.6
For numbering, see Scheme 1. In C6D6 relative to Me& (6 0): 67.80 MHz. For numbering, see Scheme 2. CH3(C5): 6 14.2 (ll),14.2 (12). 14.3 (13).CCH3(C1): 6 16.8 (ll’),17.8 (12’).dNot observed.
detection) allowed us t o measure W5N1H) = 79 f 1 Hz for compound 516(Scheme 1). This value is typical for an -NH function, and it is inconsistent with an agostic structure, which can also be ruled out from the X-ray structural study (vide infra). A triplet signal downfield (6 -4.7) for H1 and a doublet of doublets for H2 (6 -4.2) show coupling constants J 1 , 2 = 3.0 Hz, upon irradiation of the broad NH signal at high field, and J 2 , 3 = 9 Hz indicating that H1 and H2 are oriented in a syn fashion, whereas H2 and H3 are anti to one another. Irradiation of the H2 resonance at 4.14 ppm for complex 5 led to the collapse of the triplet a t 4.54 ppm to a doublet (J(H1NH) = 4.0 Hz) and collapse of the multiplet at 6 0.42 ppm for H3 to a triplet ( J I: 7 Hz). NMR spectral assignments for the other compounds could be obtained through doubleresonance techniques (lH-lH and lH-13C shift-correlated 2D spectra (see Experimental Section). The lH NMR spectrum of 2 is also characterized by a broad NH signal a t high field (6 -2) and a doublet at 2.18 ppm for the syn-methyl group. The assignments for the amine residue were obtained by the combined use of lH-’H and lH-13C shift-correlated 2D spectra (Tables 1 and 2). The 13C NMR spectrum of 2 reveals a structure similar to that of the [l-(diphenylphosphin0)(2-4-v3)-pentenylltricarbonylmanganese complex (3). The allylic chemical shifts for 2 are found downfield compared with those for the corresponding phosphino complex 3.5 In both compounds C3 shows a substantial high-field shift (6 48.6 and 46.9, respectively),as a result of the “pseudo-ring” structure. Such signals, as previously reported5 for typical substituted “allyl” systems, have 6 values of -70 ppm.17 The steric effect of these pseudo-ring structures can perhaps also be recognized by comparing the corresponding C3 value from a higher ring size compound, such as Mn[P(Ph)2CH2CH2-v3CHCHCH21(C0)3(9; 6 74.8 ppmh5
Structural Results and Discussion Analysis of the X-ray diffraction data for complexes 5 and 6 reveals that these complexes are structurally
similar to the secondary amine derivatives, such as (1pyrrolidyl-~3-pentenyl)tricarbonylmanganese ( 7 )and (1piperidyl-~3-pentenyl)tricarbonylmanganese (8). Structural parameters are essentially identical for 5 and 8. ORTEP diagrams of 5 and 6 with their atom-numbering schemes appear in Figures 1 and 2, while atomic coordinates are listed in Tables 4 and 5 and bond (16)Wrackmeyer, B. Personal communication. (17)Oudeman, A.; Sorensen, T. S. J.Organomet. Chem. 1978,156, 259.
C8
Figure 1. Molecular structure of compound 5.
07
Figure 2. Molecular structure of compound 6. distances and bond angles are in Table 6. Similar to 7 and 8, the solid-state structures of 5 and 6 may be regarded as distorted octahedral, in which the aminopentenyl ligand is bonded to a manganese center through an v3interaction and also by the nitrogen lone pair coordination. The nitrogen atom is bonded in such a way as t o yield a cis aza diene fragment, which likely optimizes its interaction with respect t o the allyl fragment, leading to an 18-electron complex. The coordination spheres of the manganese atoms are completed with three carbonyl groups in a fac arrangement. Some shortening of the manganese-nitrogen distance was observed for 5 (2.068(2)h as compared to those in 6 (2.105(7)&, 7 (2.102(7)&, and 8 (2.144(6)h3 The v3pentenyl fragment is not symmetrically bonded to the metal, as observed from Mn-C1 = 2.050(3) and 2.050(1) A,Mn-C2 = 2.115(4) and 2.14(1) A,and MnC3 = 2.192(4) and 2.187(9) A for complexes 5 and 6,
1050 Organometallics, Vol. 14,No.2, 1995
Paz-Sandoualet al.
Table 3. Crystal Data, Summary of Data Collection, and Structure Refinement for 2 , 5 , and 6 2
6
5
cryst color Z Dexptl, g
(1) Crystal Data 0.37 x 0.16 x 0.08 C14H2oMnN03 305.258 orthorhombic P2 I212 1 7.449(5) 12.572(2) 16.350(3) 90.0 90.0 90.0 1531.15 yellow 4 1.324
10.308(3) 10.935(2) 12.359(2) 90.0 110.56(2) 90.0 1304.39 yellow 4 1.350
radiation, 8, mode 28 limits, deg scan width, deg no. of rflns measd % min transmissn % max transmissn
(2) Data Collection L(Mo Ka) = 0.709 30 8-28 4-50 1.0 0.35 tan 8 1619 92.55 99.36
L(Mo K a ) = 0.709 30 8-28 4-50 1.0 0.35 tan 8 2565 85.12 99.89
L(Cu K a ) = 1.541 78 8-28 4-130
1614 193 0.0306 0.0324 0.6747 0.003
1037 154 0.0524 0.0569
cryst size, mm stoichiometry mol wt cryst syst space group
A b, A c, '4
a,
a, deg
A deg
Y,deg
v,A3
+
0.27 x 0.24 x 0.15 C II H I ~ M ~ N O ~ 265.193 monoclinic
0.21 x 0.18 x 0.12 C I 2H18MnN03 279.22 orthorhombic Pbca 7.197(1) 18.879(2) 20.561(3) 90.0 90.0 90.0 2793.83 yellow 8 1.328
P21Ic
+
2754
(3) Structure Refinement no. of rflns for final refinement no. of params refined
1046 172 0.0402 0.0460 1.3010 0.002
WF), Rw, % goodness of fit A/u (max)
Table 4. Fractional Atomic Coordinates and Equivalent Isotropic Thermal Parameters for Complex 5" atom
X
Y
Z
B (A2)
Mn 01 02 03 N c1 c2 c3 c4 c5 C6 c7 C8 c9 c10 c11
0.65838(5) 0.6600(3) 0.9129(3) 0.5157(3) 0.4948(2) 0.58 14(3) 0.7174(3) 0.7606(3) 0.9110(4) 0.9410(5) 0.3466(3) 0.2892(4) 0.2658(4) 0.6606(4) 0.8143(3) 0.5672(3)
0.21342(5) 0.0102(3) 0.3234(3) 0.3963(2) 0.1742(2) 0.2654(3) 0.2281(4) 0.1113(4) 0.0777(4) -0.0364(6) 0.2059(3) 0.1221(4) 0.1990(5) 0.0892(3) 0.2792(4) 0.3227(3)
0.8 1546(4) 0.97 18(2) 0.9746(3) 0.9075(2) 0.6653(2) 0.6453(3) 0.6685(3) 0.7153(3) 0.7555(4) 0.8254(5) 0.6414(3) 0.7 103(3) 0.5 129(4) 0.9107(3) 0.9 120(3) 0.8692(3)
3.444(9) 6.77(8) 7.99(9) 5.14(6) 3.55(6) 4.02(7) 4.23(8) 4.50(8) 6.1(1) 10.4(2) 4.35(8) 5.8(1) 6.5(1) 4.50(8) 4.98(9) 3.79(7)
Atoms refined anisotropically are given in the form of the isotropic equivalent displacement parameter, defined as 4 / 3 [ a 2 B ~ ~b2B22 -t c2&3 &(cos y)B12 ac(cos p)BI3 bc(cos a)B23]. ii
+
+
+
+
respectively. Bond distances in the N-Cl-C2-C3 fragments for complexes 5 and 6 reflect some charge delocalization, as also observed for the secondary amine derivative^.^ The structural similarities between the aminopentenyl complexes obtained from primary and secondary amines are also evident from their torsion angles. It has been found that the torsion angles C6N-C1-C2 (-179.35(27)") for 5 and C9-N-Cl-C2 (-169.9(10)") for 6 as well as C7-N-Cl-C2 for 7 (170.5(9)") and 8 (169.0(8)")3 reveal nearly planar delocalized systems, while H-N-C1-C2 for 5 (-48.2(27)") and 6 (39.6") as well as C6-N-Cl-C2 for 7 (-65.5(11)") and 8 (-62.2(10)"13 indicate much less planar systems. The structure of compound 2 is presented in Figure 3, and pertinent bonding parameters are given in Tables
c12
03
Figure 3. Molecular structure of compound 2. Table 5. Fractional Atomic Coordinates and Equivalent Isotrooic Thermal Parameters for Comdex 6n ~
~~~~
~~
atom
X
Y
Mn 06 07 08 N c1 c2 c3 c4 c5 C6 c7 C8 c9 C10 c11 C12
0.2157(2) 0.5716(8) 0.179(1) 0.4588(9) 0.0235(9) 0.085(1) 0.041(4) -0.036(1) -0.051(1) -0.050(2) 0.425(1) 0.194(1) 0.359(1) 0.028(1) -0.019(2) 0.225(1) -0.114(1)
0.24026(6) 0.3150(3) 0.2163(4) 0.1180(3) 0.3215(3) 0.2882(5) 0.2146(4) 0.1818(4) 0.1011(4) 0.0696(5) 0.2902(4) 0.2258(5) 0.1658(4) 0.4011(4) 0.4149(5) 0.4288(5) 0.4326(5)
a
~
~
~ _ _ _
B
0.12439(7) 0.1260(4) 0.2644(3) 0.1086(4) 0.1045(3) 0.0473(5) 0.0436(4) 0.0982(4) 0.1007(6) 0.1669(6) 0.1266(5) 0.2095(4) 0.1149(5) 0.1134(5) 0.1829(6) 0.0969(8) 0.0673(6)
(A2)
2.37(2) 5.6(2) 7.0(2) 5.6(2) 2.4(1) 3.4(2) 2.7(2) 3.0(2) 4.6(2) 5.4(3) 3.5(2) 3.7(2) 3.5(2) 4.0(2) 6.7(3) 8.0(4) 4.9(3)
See footnote in Table 4.
7 and 8. This related structure exhibits a more distorted octahedral geometry, due t o the steric require-
Reactions of Amines with Pentadienyl-Mn(C0)3
Organometallics, Vol. 14, No. 2, 1995 1051
Table 6. Bond Lengths (A) and Bond Angles (deg) in Complexes 5 and 6 5 Mn-N Mn-Cl Mn-C2 Mn-C3 Mn-C9 Mn-C10 Mn-C11 01-C9 02-c10 03-Cll N-C1 N-C6 Cl-C2 C2-C3 c3-c4 c4-c5 C6-C7 C6-C8 C6-C9 N-Mn-C1 N-Mn-C2 N-Mn-C3 N-Mn-C9 N-Mn-C10 N-Mn-C11 Cl-Mn-C2 Cl-Mn-C3 Cl-Mn-C9 C1-Mn-ClO C1-Mn-Cl1 C2-Mn-C3 C2-Mn-C9 C2-Mn-C10 C2-Mn-C11 C3-Mn-C9 C3-Mn-ClO C3-Mn-Cll C9-Mn-ClO C9-Mn-C11 C10-Mn-C11 Mn-N-C1 Mn-N-C6 Cl-N-C6 Mn-C1-N Mn-Cl-C2 N-Cl-C2 Mn-C2-C1 Mn-C2-C3 Cl-C2-C3 Mn-C3-C2 Mn-C3-C4 c2-c3-c4 c 3 -c4-c5 Mn-C9-01 Mn-C 10-02 Mn-C11-03 N-C6-C7 N-C6-C8 C7-C6-C8
2.068(2) 2.050(3) 2.115(4) 2.192(4) 1.793(4) 1.782(3) 1.786(4) 1.149(5) 1.146(4) 1.154(4) 1.416(4) 1.49l(4) 1.390(4) 1.408(5) 1.499(5) 1.487(8) 1.506(6) 1.514(5) 40.2(1) 68.6( 1) 77.9(1) 104.5(1) 160.7(2) 95.9( 1) 39.0(1) 69.6(1) 142.6(1) 120.5(2) 97.5(1) 38.1(1) 132.9(2) 94.6(2) 128.O( 1) 95.0(2) 94.8(2) 166.1(1) 93.8(2) 98.6(2) 87.1(2) 69.2(1) 125.8(2) 117.8(3) 70.6(2) 73.1(2) 114.2(3) 68.0(2) 73.9(2) 120.1(3) 68.0(2) 125.8(3) 120.0(3) 112.2(4) 178.9(4) 178.6(4) 176.0(3) 109.0(3) 110.1(3) 112.4(3)
Mn-N Mn-C1 Mn-C2 Mn-C3 Mn-C7 Mn-C8 Mn-C6 07-C7 08-C8 06-C6 N-Cl N-C9 c 1-c2 C2-C3 c3-c4 c4-c5 C9-C10 C9-C11 C9-Cl2 N-Mn-CI N-Mn-C2 N-Mn-C3 N-Mn-C7 N-Mn-C8 N-Mn-C6 Cl-Mn-C2 Cl-Mn-C3 Cl-Mn-C7 Cl-Mn-C8 C1 -Mn-C6 C2-Mn-C3 C2-Mn-C7 C2-Mn-C8 C2-Mn-C6 C3-Mn-C7 C3-Mn-C8 C3-Mn-C6 C7-Mn-C8 C6-Mn-C7 C6-Mn-C8 Mn-N-C1 Mn-N-C9 Cl-N-C9 Mn-C1-N Mn-C1 -C2 N-Cl -C2 Mn-C2-C1 Mn-C2-C3 Cl-C2-C3 Mn-C3-C2 Mn-C3-C4 c2-c3-c4 c3-c4-c5 Mn-C7-07 Mn-C8-08 Mn-C6-06 N-C9-C10 N-C9-C11 N-C9-C12 ClO-C9-C11 ClO-C9-C12 Cll-C9-C12
Table 7. Fractional Atomic Coordinates and Equivalent Isotropic Thermal Parameters for Complex 2a
6
atom
X
2.105(7) 2.05(1) 2.14( 1) 2.187(9) 1.78(1) 1.76(1) 1.781(7) 1.15(1) 1.16(1) 1.15(1) 1.41(1) 1.51(1) 1.43(1) 1.40(1) 1.53(1) 1.48(2) 1.49(2) 1.54(1) 1.52(2)
Mn 01 02 03 N c1 c2 c3 c4 c5 C6 c7 C8 c9 c10 c11 c12 C13 C14
0.93OO( 1) 1.2242(7) 1.2188(8) 0.93 12(7) 0.7255(6) 0.701(1) 0.7832(9) 0.8045(8) 0.690( 1) 0.703 1) 0.9325(8) 1.101(1) 1.1059(9) 0.7604(9) 0.817(1) 0.860( 1) 0.701(1) 0.639( 1) 0.5960(9)
39.6(3) 68.2(3) 77.1(3) 104.1(4) 161.6(4) 100.1(4) 39.7(4) 69.8(4) 141.9(4) 122.4(5) 100.0(4) 37.7(4) 132.7(4) 94.5(4) 129.6(5) 95.2(5) 93.3(4) 167.2(5) 92.2(5) 97.5(6) 85.8(4) 39.6(3) 133.2(6) 122.5(8) 72.2(5) 73.3(5) 114.1(8) 67.0(5) 73.1(5) 118.6(8) 69.2(5) 123.5(7) 119.8(9) 115(1) 180(1) 177.9(8) 172(1) 106.5(8) 109.3(8) 107.3(8) 111(1) llO(1) 112.1(9)
ments of the aminopentenyl ligand. The cyclohexylamine group is bonded to the pentadienyl group, leading to a l-(cyclohexylamino)-(2-4-~3)-pentenylfragment corrdinated through the nitrogen atom and the allyl moiety to the manganese atom. One can see that the structure is generally similar to that for the phosphorus analog, 3.5 However, some differences in bond lengths between 2 and 3 require comment. While compound 2 has an Cl-C2 allylic bond longer than the corresponding C2-C3 bond (1.43(1) us 1.366(9)A), the phosphino
Y 0.75417(8) 0.907 l(4) 0.5953(4) 0.7171(4) 0.8706(3) 0.6435(5) 0.6664(5) 0.7673(5) 0.8583(5) 0.5323(6) 0.7357(5) 0.6569(5) 0.8523(5) 0.9853(5) 0.9890(5) 1.1063(5) 1.1781(6) 1.1712(6) 1.0550(5)
Z
B (A2)
0.15190(5) 0.1726(4) 0.1611(3) -0.0256(2) 0.1538(3) 0.1642(4) 0.241 l(4) 0.2708(3) 0.2430(4) 0.1296(4) 0.0433(3) 0.1607(4) 0.1641(4) 0.1298(4) 0.041 l(4) 0.0167(4) 0.0310(5) 0.1208(4) 0.1429(4)
3.05(1) 7.3(1) 6.6(1) 5.6(1) 2.6(1) 4.3(2) 4.0(2) 3.8(1) 4.3(2) 5.4(2) 3.5(1) 4.0(2) 4.5(2) 3.3(1) 4.7(2) 6.0(2) 6.4(2) 5.2(2) 3.9(1)
See footnote in Table 4.
Table 8. Bond Lengths (A) and Bond Angles (deg) in Complex 2 Mn-N Mn-C1 Mn-C2 Mn-C3 Mn-C6 Mn-C7 Mn-C8 01-03 02-C7 03-C6 N-C4 N-Mn-C1 N-Mn-C2 N-Mn-C3 N-Mn-C6 N-Mn-C7 N-Mn-C8 Cl-Mn-C2 Cl-Mn-C3 Cl-Mn-C6 Cl-Mn-C7 Cl-Mn-C8 C2-Mn-C3 C2-Mn-C6 C2-Mn-C7 C2-Mn-C8 C3-Mn-C6 C3-Mn-C7 C3-Mn-C8 C6-Mn-C7 C6-Mn-C8 C7-Mn-C8 Mn-N-C4 Mn-N-C9
2.1 12(5) 2.213(8) 2.131(6) 2.163(6) 1.791(6) 1.774(9) 1.81l(9) 1.127(9) 1.17(1) 1.15l(6) 1.489(9) 83.0(2) 88.8(3) 67.8(3) 96.4(3) 174.5(4) 92.8(3) 38.4(3) 68.4(3) 9 1.0(3) 96.6(3) 167.7(5) 37.1(3) 128.1(3) 87.5(3) 130.4(4) 154.9(3) 106.9(4) 99.3(3) 89.1(4) 100.9(4) 86.5(3) 94.0(4) 122.1(4)
N-C9 Cl-C2 C1-C5 C2-C3 c3-c4 C9-C10 C9-Cl4 ClO-c11 Cll-c12 C12-Cl3 C13-Cl4 C4-N-C9 Mn-Cl-C2 Mn-Cl-CS C2-Cl-C5 Mn-C2-C1 Mn-C2-C3 Cl-C2-C3 Mn-C3-C2 Mn-C3-C4 c2-c3-c4 N-C4-C3 Mn-C6-03 Mn-C7-02 Mn-C8-01 N-C9-C10 N-C9-C14 ClO-C9-C14 c9-c1o-c11 ClO-C11-C12 c 1l - c l 2 - c l 3 C12-Cl3-Cl4 C9-Cl4-Cl3
1.517(8) 1.43(1) 1.51(1) 1.366(9) 1.50(1) 1.512(9) 1.52l(9) 1.560(9) 1.50(1) 1.54( 1) 1.538(8) 112.5(5) 67.7(4) 122.1(6) 120.5(8) 73.9(4) 72.7(4) 123.3(6) 70.2(4) 91.8(4) 122.4(6) 106.0(5) 175.5(6) 175.1(9) 174.7(8) 109.0(5) 111.9(5) 110.0(6) 109.4(5) 111.6(6) 110.5(6) 109.9(6) 110.2(5)
analogue complex 3 shows the opposite trend (1.38(1) us 1.45(1) A). The difference in 2 is also accompanied by a difference in the Mn-C1,3 bond lengths (2.213(8) us 2.162(6) A), which is not as significant as the difference found for 3 (2.245(8) us 2.356(8) A).5 The torsion angles found for Cl-Mn-N-C4 (73.4(4)")and Cl-Mn-P-C4 (65.6(4)"),along with the corresponding Mn-N-C4-C3 (-5.4(5)") and Mn-P-C4-C3 (+0.7(4)") values, all seem to reflect the differing steric requirements for the nitrogen and phosphorus compounds. Thus, it appears that the strain induced by coordination of the enyl-amine ligand is much lower than that resulting for the analogous enyl-phosphine complex 3. In fact, the substituted-allyl distortion
1052 Organometallics, Vol. 14,No. 2, 1995
decreases from 3 > 2 > 9.18 From the above results, as well as from the observation of similar 13C chemical shifts for C3 in complexes 2 (6 48.6) and 3 (6 46.91,it is clear that a partial a-allyl coordination mode does not contribute significantly in complex 2 and, therefore, the strain effect on this pseudo-ring structure is predominant.
Acknowledgment. Financial support from the CONACYT/NSF is gratefully acknowledged. We thank Prof. (18)This is judged by a comparison of the various torsion angles and C-C bond distances in the delocalized-organic fragment. (19) Kreiter, C. G.;Leyendecker, M. J . Organomet.Chem. 1985,280, 225.
Paz-Sandoval et al.
Dr. Bernd Wrackmeyer, Laboratorium fiir Anorganische Chemie, Universitat Bayreuth, for stimulating discussions and also for performing the inverse detection IH NMR spectrum.
Supplementary Material Available: Listings of positional parameters, general displacement parameter expressions, bond distances, bond angles, least-squares planes, and torsion angles for 2,5, and 6 (24 pages). Ordering information is given on any current masthead page. OM9408800
