Further chemistry of trimethylphosphine complexes of rhodium(I): X-ray crystal structures of dodeca(trimethylphosphine)tetrarhodiumhexamercury, Hg6Rh4(PMe3)12, and trans-chlorobis(trimethylphosphine)(triphenylphosphine)rhodium(I)

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Abstract
The interaction of sodium amalgam in tetrahydrofuran with [Rh(PMe3)4]Cl or RhCl(PMe3)3 yields Hg6Rh4(PMe3)12(1) in high yields. Similar reduction of [RhH2(PMe3)4]Cl yields RhH(PMe3)4(2) and RhCl(CO)(PMe3)2 gives [RhH(CO)(PMe3)3]2, (3). The syntheses of the following complexes are also reported: RhCl(PMe2Ph)(PMe3)2, (4), Rh(η-C5H5)(PMe3)2, (5), RhMe(PMe3)3, (6), Rh(C6H4Me-3)(PMe3)3, (7), RhCllMe(PMe3)3, (8), RhCll(C6H5)(PMe3)3, (9), [Rh (O2)(PMe3)4]PF6, (10), and trans-RhCl(PPh3)(PMe3)2, (11). The compounds have been studied by 1H and 31P n.m.r. and i.r. spectroscopy and the structures of (1) and (11) have been determined by X-ray crystallography. Complex (1) is orthorhombic, space group Ccmm or Ccm2, with a= 12.909(2), b= 25.274 (4), c= 25.176(4)Å, and Z= 4. Complex (11) is monoclinic, space group P21/n, with a= 17.006(3), b= 11.821(2), c= 12.884(2)Å, β= 96.46(2)°, and Z= 4. The structures were determined using 2 448 and 3 708 observed intensities measured on an automatic diffractometer and refined to R values of 0.083 and 0.038 respectively. For compound (1) only the Hg, Rh, and P atom positions could be determined with any certainty. The Hg6Rh4P12 cluster has the form of an Hg6 octahedron with four tetrahedrally related faces capped by Rh(PMe3)3 units; Hg–Hg and Hg–Rh distances lie in the ranges 3.131(3)–3.149(3)Å and 2.690(4)–2.724(4)Å respectively. Compound (11) has the PPh3 groups trans to the chloride. Bond distances and angles are similar to those in the tris PPh3 and PMe3 analogues.

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