Complexes of Distibinomethane Ligands. 1. Iron, Cobalt, Nickel, and Manganese Carbonyl Complexes

Abstract

The reaction of Fe 2 (CO) 9 in thf with Ph 2 SbCH 2 SbPh 2 (dpsm) or Me 2 SbCH 2 SbMe 2 (dmsm) produced [Fe(CO) 4 (η 1 -dpsm)] and [Fe(CO) 4 (μ-dmsm)Fe(CO) 4 ], and Co 2 (CO) 8 reacted with either distibine ligand (L-L) to give [Co 2 (CO) 4 (μ-CO) 2 (μ-L-L)]. Ni(CO) 4 and dpsm gave [Ni(CO) 3 (η 1 -dpsm)] and [Ni(CO) 3 (μ-dpsm)Ni(CO) 3 ], while with dmsm only [Ni(CO) 3 (μ-dmsm)Ni(CO) 3 ] was isolated. Mn 2 (CO) 10 reacted slowly with dpsm or dmsm in the presence of a [{(Cp)Fe(CO) 2 } 2 ] catalyst to give [Mn 2 (CO) 8 (L-L)], but no reaction occurred with Re 2 (CO) 10 under similar conditions. cis- [Mn(CO) 4 X(dpsm)] (X = Cl, Br, or I) and [Mn 2 (CO) 8 Br 2 (μ-dmsm)] were also prepared from the appropriate [Mn(CO) 5 X], but iron carbonyl halide derivatives were too unstable to isolate in the pure state. The complexes have been characterized by elemental analysis, IR and multinuclear NMR ( 1 H, 13 C{ 1 H}, 55 Mn, or 59 Co) spectroscopy, and FAB mass spectrometry. The X-ray structures of dpsm, [Fe(CO) 4 (η 1 -dpsm)], and [Co 2 (CO) 4 (μ-CO) 2 (μ-dmsm)] have been determined. No evidence for chelation by dmsm or dpsm was found, and Sb−C fission does not occur to significant extents in the reactions studied.