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

The reaction of Fe<INF>2</INF>(CO)<INF>9</INF> in thf with Ph<INF>2</INF>SbCH<INF>2</INF>SbPh<INF>2</INF> (dpsm) or Me<INF>2</INF>SbCH<INF>2</INF>SbMe<INF>2</INF> (dmsm) produced [Fe(CO)<INF>4</INF>(η¹-dpsm)] and [Fe(CO)<INF>4</INF>(μ-dmsm)Fe(CO)<INF>4</INF>], and Co<INF>2</INF>(CO)<INF>8</INF> reacted with either distibine ligand (L-L) to give [Co<INF>2</INF>(CO)<INF>4</INF>(μ-CO)<INF>2</INF>(μ-L-L)]. Ni(CO)<INF>4</INF> and dpsm gave [Ni(CO)<INF>3</INF>(η¹-dpsm)] and [Ni(CO)<INF>3</INF>(μ-dpsm)Ni(CO)<INF>3</INF>], while with dmsm only [Ni(CO)<INF>3</INF>(μ-dmsm)Ni(CO)<INF>3</INF>] was isolated. Mn<INF>2</INF>(CO)<INF>10</INF> reacted slowly with dpsm or dmsm in the presence of a [{(Cp)Fe(CO)<INF>2</INF>}<INF>2</INF>] catalyst to give [Mn<INF>2</INF>(CO)<INF>8</INF>(L-L)], but no reaction occurred with Re<INF>2</INF>(CO)<INF>10</INF> under similar conditions. cis-[Mn(CO)<INF>4</INF>X(dpsm)] (X = Cl, Br, or I) and [Mn<INF>2</INF>(CO)<INF>8</INF>Br<INF>2</INF>(μ-dmsm)] were also prepared from the appropriate [Mn(CO)<INF>5</INF>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 (¹H, ¹³C{¹H}, ⁵⁵Mn, or ⁵⁹Co) spectroscopy, and FAB mass spectrometry. The X-ray structures of dpsm, [Fe(CO)<INF>4</INF>(η¹-dpsm)], and [Co<INF>2</INF>(CO)<INF>4</INF>(μ-CO)<INF>2</INF>(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.