Synthesis and reactivity of(mu - H)(mu _3 - eta ^2 - H_2 )_4 )Os_3 (CO)_9 : An unusually reactive triosmium cluster |
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Authors: | Shariff E. Kabir Edward Rosenberg Michael Day Kenneth I. Hardcastle Mark Irving |
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Affiliation: | 1. Department of Chemistry, University of Montana, 59812, Missoula, MT 2. Department of Chemistry, California State University at Northridge, 91330, Northridge, CA
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Abstract: | The synthesis of $(mu - H)(mu - eta ^2 - H_2 )_4 )Os_3 (CO)_{10} $ (4) from piperidine and Os3(CO)10(CH3CN)2 and its solid state structure are reported. The room temperature reactions of the decarbonylation product of4, $(mu - H)(mu _3 - eta ^2 - H_2 )_4 )Os_3 (CO)_9 $ (3), with P(C6H5)3, CNCH3, HCl and H2 are reported. Overall, the products obtained closely resemble those obtained from the analogous, $(mu - H)(mu _3 - eta ^2 - H_2 )_3 )Os_3 (CO)_9 $ (1). The isomerizations of the phosphine addition products $(mu - H)(mu - eta ^2 - H_2 )_n )Os_3 (CO)_9 P(C_6 H_5 )_3 $ (n = 3,6a;n = 4,5a) have been studied by1H-NMR techniques and the initial rearrangement was shown to be an intramolecular process. Slower conversion to the complex $(mu - H)(mu _3 - eta ^2 - H_2 )_4 )Os_3 (CO)_8 P(C_6 H_5 )_3 $ (8) was observed and the solid state structure of this product is reported and compared with a related compound containing an ethyl,n-propylμ 3-imidoyl ligand. Compound4 crystallizes in the triclinic space group Pl (#2) withZ= 2, and unit cell parametersa = 9.294(3) Å,b = 15.758(5) Å,c = 7.406(2) Å,a = 81.10(2)°,β=76.47(2)°,y =74.88(2)°, andV =1013(l) Å3. Least-squares refinement of 2677 reflections gave a final discrepancy factor ofR = 0.054 (R w = 0.066). Compound8 crystallizes in the space group C2/c with unit cell parametersa = 24.818(3) Å,b = 16.389(3) Å,c = 18.111(3) Å,β= 120.94(2)°,V = 6318(4) Å3, andZ = 8. Least squares refinement of 3439 reflections gave a final discrepancy factor ofR = 0.039 (R w =0.047). |
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