Organometallics 1991,10, 3550-3559
3550
Phosphine Addition and Substitution Reactions on Unusually Reactive Triosmium Clusters: (p-H)(p3-q2-C= NCH2CH2CH2)Os3(CO)9and (p-H) (E . ( . ~ - ~ ~ - C H ~ C H ~ C = N C H ~ C H C0)g ~CH~)OS~( Michael Day, David Espitia, Kenneth I . Hardcastle, Shariff E. Kabir, and Edward Rosenberg' Department of Chemistty, California State University, Northridge, California 9 1330
Roberto Gobetto, Lucian0 Milone, and Domenico Osella Dipartimento di Chimica Inorganica, Chimica Fisica e Chimica dei Materiali, Universiti di Torino, Via Giuria 7-9, I 10 125 Torino, Italy Received April 4, 199 1 I
The reactions of (p-H)(p3-q2-C=NCHzCH2CHz)Os3(CO)g (11, (p-H)(p3-v2-CH3CH2C=NCH2CH2CH3), I O S ~ ( C O(2), ) ~ (p-H)(p-q2-C=NCH2CHzCH~Os3(CO)lo (31, and (p-H)(p-q2-CH3CH2C=NCH2CH2CH3)O S ~ ( C O(4) ) ~with ~ trialkylphosphines at 25-100 "C have been studied. At room temperature 1 gives a phosphine addition product (~L-H)(~-~~-C=NCH~CH~CH~)OS~(CO)~(C~H~)~ (5) where the phosphine has added to the metal atom formerly r-bound to the C=N bond of the p3-imidoyl ligand; 5 exists as two isomers in solution. Compound 5 rearranges to the isomeric 6a and 6b at 100 "C in which the phosphine is at one of the two metal atoms bridged by the hydride and the imidoyl ligand. At 100 OC 3 substitutes phosphine for carbonyl to also give 6a and 6b, which on further thermolysis at 125 "C decarbonylate to give (p4 H)(p3-q2-C=NCHzCHzCH2)Os3(CO)gP(C6H5)3 (7). In contrast, reaction of 2 with triphenylphosphine at room temperature gives (p-H)(p-q2-CH3CH2C=NCH2CH2CH3)O~3(C0)9P(C6H5)3) (8), which exists as a mixture of five of six possible positional isomers with respect to location of the phosphine, hydride, and imidoyl ligands in solution. The reaction of 4 with triphenylphosphine at 100 "C gives this same mixture of isomers. Decarbonylation of 8 proceeds at 125 "C to give (p-H)(p3-q2-CH3CHzC=NCH2CH2CH3)0s3(CO)8P(CBH.$3)(9) and the dihydrido orthometalation product (p-H)z(p-v2-CH3CHzC=NCH2CH2CH3)Os3(CO),(p-q -(C6H5)2P(~-C6H4)) (10). Reaction of 2 with trimethylphosphine or trimethyl phosphite gives (R= CH3, 11;R = OCH3, 121, the addition products (~-H)(P-~~-CH~CH~C=NCH~CH~CH~)OS~(CO)~PR~ which are structurally analogous to 5 in solution. The origin of the structural differences between the addition products obtained from the reaction of 1 and 2 with P(C6H5I3and from 2 with the different phosphorous ligands is discussed in terms of steric interactions between the imidoyl ligand and the phosphorous ligand. All compounds reported were characterized by 'H NMR,infrared spectroscopy, and elemental analysis. In addition, solid-state-structures for 5, 6a, 8a, and 9 were determined. Compound 5 crystallizes in the triclinic space group P1 (No.2) with unit cell parameters a = 10.762 (2) A, b = 17.442 (2) A, c = 8.595 (2) A, a = 97.38 (1)O, @ = 94.04 (1)O, y = 97.44 (1)O, V = 1580 (1)A3,and 2 = 2. Subsequent least-squares refinement of 5058 reflections gave a final agreement factor of R = 0.032 (R, = 0.041). Compound 6a crystallizes in the monoclinic space group E1/c(No. 14) with unit cell parameters a = 9.307 (2) A, b = 15.601 (3) A, c = 21.773 (4) A, @ = 97.59 ( 2 ) O , V = 3134 (2) A3,and 2 = 4. Least-squares refinement of 4316 reflections gave a final agreement factor of R = 0.029 (R, = 0.036). Compound 8a crystallizes in the triclinic space group P1 (No.2) with unit cell parameters a = 12.684 (3) A, b = 16.254 (3) A, c = 9.561 (2) A, a = 99.53 (1)O,@ = 96.69 (2)O, y = 112.57 (2) A, V = 1760 (1)A3,and 2 = 2. Least-squares refinement of 4236 reflections gave a final agreement factor of R = 0.031 (R, = 0.038). Compound 9 crystallizes in the orthorhombic space group P2 2121 (No.19) with unit cell parameters a = 9.626 (1)A, b = 15.342 (2) A, c = 22.849 (3) A, V = 3374 (1) and 2 = 4. Least-squares refinement of 2841 reflections gave a final agreement factor of R = 0.031 (R, = 0.027). I
i
I
ff3,
Introduction Ligand substitution reactions on valence-saturated osmium carbonyl clusters normally take place a t elevated temperature^.'-^ Although these substitution reactions often exhibit an associative component in their rate laws and can occur with activation energies below that required for carbonyl-metal bond cleavage, the dissociation of a carbonyl ligand is always part of the rate-determining process.3b Recently, there have been several reports in the literature of valence-saturated trinuclear clusters under(1) Deeming, A. J.; Johnson, B. F. G.; Lewis, J. J. Chem. SOC. A 1970, Dalton Trans. 1973, 897. Deeming, A. J.; Underhil, M. J. Chem. SOC., 2727; Deeming, A. J.; Kimber, R. E.; Underhill, M. J. Chem. SOC., Dalton Trans. 1973, 2589. (2) Shojaie, A.; Atwood, J. D.Or anometallics 1985, 4, 187. (3) Poe, A. J.; Twigg, J. J.Chem. ~ o c .Dalton , Trana. 1974,1860. Poe, A. J.; Sekhar, V. C. Inorg. Chem. 1986,24, 4376.
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going ligand addition and substitution reactions with Phosphines and other hw-electron donors a t Or below room temperatures4-' These reactions are usually associated with cleavage of a metal-metal bond (often reversible) or (4) (a) Huttner, G.; Knoll, K. Angew. Chem., Int. Ed. Engl. 1987,26, 743 and references therein. (b) Carty, A. J.; MacLaughlin, S. A,; Taylor, N. J. J. Organomet. Chem. 1981,204, C 27. (c) Planalp, R. P.; Vahrenkampt He Organometallics 1987,61492. (5) Deeming, A. J.; Donovan-Mtunzi, S.; Kabir, S. E.; Manning, P. J. J, them, sot,, Dalton Trans, 1985, 1037, (6) (a) Mayr, A.; Lin, Y.C.; Boag, N.M.; Kampe, C. E.; Knobler, C. B.; Kaesz, H.D. Inorg. Chem. 1984,23,4646. (b) Keijsper, J.; Polm, L.
H.; van Koten, G.; Vrieze, K.; Seignette, P. F. A,; Stam, C. H. Inorg. Chem. 1985,24,518. (c) Adams, R. D.; Golembeski, N. M. J.Am. Chem. SOC. 1979,101, 2679. (d) Adams, R. D.; Katahira, D. A.; Wang, L. W. J . Organomet. Chem. 1981,229, 86. (7) (a) Lugan, N.; Lavigne, G.; Bonnet, J. J.Inorg. Chem. 1987,26,585. (b) Lugan, N.; Lavigne, G.; Bonnet, J. J.; Reau, R.; Neibecker, D.; Tkatchenko, I. J. Am. Chem. SOC. 1988, 220, 5369.
0 1991 American Chemical Society
Organometallics, Vol. 10,No.10,1991 3551
Phosphine Addition and Substitution Reactions the presence of a mobile' or cis-labilizingliganda4We have recently synthesized a range of trinuclear clusters of osmium and ruthenium with face-capping nitrogen-containing ligands that exhibit unusually high reactivity toward ligand addition and substitution reactiom8 We report here the details of our studies of the reactions of phosphines with the triosmium clusters (p-H)(p3-q2C=NCH2CH2CHz)Os3(CO)9 (1) a n d (p-H)(p3-q2CH3CH2C=NCH2CH2CH3)0s3(C0)9 (2), which are obtained in good yields from decarbonylation of (p-H)( p , I s2-C=NCH2CH2CHz)Os3(C0) (3) and (p-H)(p-q2CH3CH2C=NCH2CH2CH3)0s3(CO)lo (4), which are in turn synthesized from the reactions of pyrrolidine and di-n-propylamine with O S ~ ( C O ) , ~ ( C H ~ Crespectively N)~, (eqs 1 and 2).
Scheme I
i
u
5a
5b
Table 1. Crystal Data: Collection a n d Refinement Parameters compound 5 6a 8a 9 formula C31H22N0s- CS1H22N0s- CSHBNOS- C32H&08POs3 POs3 POsa POs3 fw 1154.10 1154.10 1184.17 1156.16 cryst syst triclinic monoclinic triclinic orthorhombic space group Pi m11c Pi m2121 a, A
3
O S ~ ( C O ) ~ O ( C H ~+C N NH(CH2CH2CH3)2 )~
-
1
2 5 4 5 "C
C , H2C H2C H3
CH3CH2,
10.762 (2) 17.442 (2) 8.595 (2) 97.38 (1) 94.04 (1) 97.44 (1) A3 1580 z 2 density,,, g/cm3 2.43 abs coeff, fi, cm-' 121.6 data collect 25 f 1
b, A c, A a,deg & deg 7,deg
,CH2CH2CH3
v,
temp, "C radiatn scan mode scan limits, deg 2
4
We have not only observed room temperature ligand addition for 1 and 2 but also a remarkable sensitivity toward the product obtained, depending on the structure of amine ligands and the steric bulk of the phosphine ligands.
Results and Discussion The reaction of 1 with triphenylphosphine a t room
scan speed, deg/min scan range, deg no. of data no. obsd no. variables R" RWb
97.59 (2) 3134 4 2.45 122.6 25 f 1
12.684 (3) 16.254 (3) 9.561 (2) 99.53 (1) 96.69 (2) 112.57 (2) 1760 2 2.23 109.2 25 f 1
9.626 (1) 15.342 (2) 22.849 (3)
3374 4 2.28 113.8 25 f 1
MoKa
MoKa
MoKa
MoKa
w-2e 4 < 28 50° 7.2-8.2
w-2e 4 < 28 48 7.2-8.2
w-2e 4 < 28 48 7.2-8.2
crr2e 4 < 28 56 7.2-8.2
3a(F,,) for each crystal are listed in Table I. All other reflections were considered to be unobserved. Each of the structures was solved by the Patterson method using SHELXS-~X,~ which revealed the positions of the metal atoms. All other non-hydrogen atoms were found by successive difference Fourier syntheses. The hydride positions were calculated by using the program Hydex.12 No other hydrogens were located. The hydride positions were included in the structure factor calculations but not refined in the final least-squares cycles. All non-hydrogen atoms were refiied anisotropically. Selected bond distances and angles are given in Tables 11-V and the residual electron densities in the final structures are listed in Table I. Scattering factors were taken from Cromer and Waber.23 (22) Sheldrick, G. M. S H E L X S - ~Program ~, for Crystal Structure Solution, University of Gottingem, 1986. (23) Cromer, D. T.; Waber, J. T. International Tables for X-ray Crystallography; Kynoch Press: Birmingham, England, 1974; Vol. IV, Table 2.2B.
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Anomalous dispersion corrections were those of C r ~ m e r .All ~~ calculations were carried out on a DEC MicroVax I1 computer, using the SDP/VAX system of programs.
Acknowledgment. We gratefully acknowledge the support of the National Science Foundation (CHE9016495) for support of this research. We thank the NATO Science Program for a travel grant (E.R. and L.M.) and the Consiglio Nazionale delle Ricerche and the Ministero dell Universita (L.M). We also acknowledge Prof. A. Fratiello and R. Perrigan at California State University, Los Angeles, for help in obtaining 400-MHz 'H NMR spectra and Johnson-Matthey for a loan of osmium tetroxide (D.O.). Supplementary Material Available: Tables 6-9,listing atomic positions, Tables 10-13, listing anisotropic displacement factors, and Tables 14-17,listing bond distances and angles for 5,6a, 8a, and 9 (29pages); Tables 18-21,listing calculated and observed structure factors for 5, 6a, 8a, and 9 (167pages). Ordering information is given on any current masthead page. (24) Cromer, D.T. International Tables for X-ray Crystallography; Kynoch Press: Birmingham, England, 1974; Vol. IV, Table 2.3.1.
Formation of Metallacyclic (Zirconoxycarbene)vanadium Complexes from CPV(CO)~and Their Conversion into Ordinary Fischer-Type Carbene Complexes of Vanadium Gerhard Erker' and Ronald Pfaff Organisch-Chemisches Instnut der Universit2it Miinster, Corrensstrasse 40, 134400 Miinster, FRG
Carl Kruger and Stefan Werner Max-Planck- Institut fik Kohlenforschung, Kaiser- Wiiheim-Pia& 1, D-4330 Miilheim a.d. Ruhr, FRG Received March 25, 199 1
(s-trans-Butadiene)zirconocene (8) adds to a carbonyl ligand of CpV(CO)( to give the [ (wally1)zirconoxycarbene]vanadium complex Cp2ZrOC[=VCp(CO)3]C4& (llb). (butadiene)HfCp, reacts similarly to give a mixture of the [ (T-allyl)hafnoxycarbene]-and seven-membered metallacyclic [ (u-a1lyl)hafnoxycarbene]vanadium species (1la/ 12a). These complexes subsequently add a ketone (acetone, acetophenone, methyl vinyl ketone), aldehyde (acrolein),or nitrile (pivalonitrile) to yield nine-membered metaloxycarbene , 1 vanadium complexes, such as CpzHfOC[=VCp(C0)3]CH2CH=CHCH2C(CH3)z0 (13a), exhibiting analogous chiral trans-cycloalkene dioxametalla-trans-cyclononeneframeworks. The (carbene)vanadiumcomplex 13a was characterized by X-ray diffraction. Complex 13a crystallizes in space group P2,lc with cell constants a = 11.741 (1)A, b = 14.244(2)A, c = 15.824 (1)A, 0 = 109.57(1)O,2 = 4,R = 0.028,R, = 0.023.Treatment of the nine-membered metaloxycarbene complexes with tetrabutylammonium fluoride trihydrate in tetrahydrofuran solution gave the Zr,Hf-free vanadium acylmetalate complexes [Cp(CO)3VC(=O)CH2CH=CHCHzCR'R20H] (NBu,), which were subsequently 0-alkylated with triethyloxonium tetrafluoroborate to yield the ordinary Fischer-type (carbenehanadium complexes Cp(CO)3V=C(OC2HJI CH2CH=CHCHzCR'R20H. Treatment of Cp2ZrOC[=VCp(C0)3]C4H6(1lb) with TBAF.3H20 followed (24). by the reaction with Meerwein's reagent gave CP(CO)~V=C(OC~H~)CH~CH=CHCH~ I
Heteroatom-stabilized carbene complexes play an important role as stoichiometric reagents in organic synthesis. They are becoming increasingly important as catalysts for the selective conversion of unsaturated organic substrates.' Carbene complexes are readily available for most transition (1) See, e.g.: Caeey, C. P.~n T r a m i t i K M e t a l Organometallics in Organic Synthesia; Alper, H., Ed.; Academic Press: New York, 1976; Vol. 1, p 190. Brown, F. J. B o g . Inorg. Chem. 1980,27,1. DBtz, K. H. Angew. Chem. 1984, W,573; Angew. Chem., Int. Ed. Engl. 1984,23,587. Schubert, U.;Fischer, H.; Hofmann, P.; Weiss, K.; DBtz, K. H.;Kreissl, F. R. Tramition Metal Carbene Complexes; Verlag Chemie: Weinheim, Germany, 1983.
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metals. However, there are a few situations where carbene complexes of neither the Fischer nor the Schrock type seem to be obtained easily. Among others, this applies for the d-block element vanadium. To our knowledge only a very limited number of heteroatom-stabilized (carbeneb vanadium complexes have been mentioned in the literature. So far, notable examples are complexes 3 and 5: both of which were prepared by synthetic routes avoiding the (2) Hartshorn, A. J.; Lappert, M. F.; Tumer, K. J. Chem. Soc., Dalton Trans. 1978, 348. Martin, J.; Moise, C.; Tirouflet, J. C. R. Hebd. Seances Acad. Sci., Ser. 2 1981,292, 1143.
0 1991 American Chemical Society
