Synthesis and Crystal Structure of Tetranuclear Cobalt Carbonyl Clusters

Abstract

Abstract: The reactions of Co₂(CO)₈ with organic cyclic dithiophosphinate SP(S)(C₆H₄OR)N(C₆H₅)NC(Me)(R=Me, Et) gave four tetranuclear cobalt carbonyl clusters containing capping S, Pbridging ligand in Co 4(CO)₁₀ (μ₄-S) (μ₄-PC₆H₄OR)(1: R=Me, 3: R=Et) and P⌒Cbridging and face bridging Sligand in Co₄ (CO)₁₀ (μ₃-S)[μ₂-P(C₆H₄OR)N(Ph)NCMe](2:R=Me, 4:R=Et). During the reactions, the two ligand precursors have cleaved in its PSand/or C-S, P-S, P-Nbonds respectively to give the fragments as the ligand as listed above that coordinated to Co atoms to form the new cluster molecules. These clusters have characterized by elementary analysis, IR, ¹H NMRand MSspectroscopy. The crystal structure of cluster 4 has been determined by X-ray diffraction techniques. The crystal belongs to monoclinic with space group P2₁/c. The cell parameters are as follows: a=1.9065(4) nm, b=1.0081(2) nm, c=1.6663(3) nm, β=97.36(3)°, V=3.1704(11) nm³, D_c=1.743 g/cm³, Z=4. The Co-Co average bond length is 0.251 nm in the triangular plane of Co1Co3Co4, the Co2 is linked on the plane to form a spike. The tetracobalt framework is "spiked triangular". The stereogeometry of each Co assumes a distorted octahedron with different coordination environments.

Key words: Cobalt carbonyl cluster, Cleavage and combination synthesis method, Crystal structure

CLC Number:

O614.812

TrendMD:

WU Bing-Fang, ZHANG Fu-Qiang, LIU Shu-Tang, HU Xiang, JIN Xiang-Lin. Synthesis and Crystal Structure of Tetranuclear Cobalt Carbonyl Clusters[J]. Chem. J. Chinese Universities, 2002, 23(8): 1470.

References

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