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DOI: 10.1039/A902481F (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 3191-3195

The synthesis and structure of a paramagnetic Lewis base adduct of antimony pentachloride, trans-[MnII(CNSbCl5)(CO)2{P(OEt)3}(dppm)][SbCl6][hair space]†

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Dena Bellamy, Nathan C. Brown, Neil G. Connelly and A. Guy Orpen

Abstract

Treatment of cis-[Mn(CN)(CO)2{P(OEt)3}(dppm)] with SbCl5 gave paramagnetic trans-[Mn(CNSbCl5)(CO)2{P(OEt)3}(dppm)][SbCl6] the crystal structure of which shows the geometry of the [Mn(CN)(CO)2{P(OEt)3}(dppm)] fragment to be characteristic of a low-spin manganese(II) centre. The Mn–P(OEt)3 and Mn–Pdppm bond lengths are increased by 0.10 and 0.07 Å compared with those in analogous manganese(I) species while the Mn–C distances are little changed. A Cambridge Structural Database study of octahedral L·SbCl5 species indicated that the Sb–Cl distances (cis and trans to the ligand L) and the average L–Sb–Clcis angle are strongly correlated and appear to reflect the donor ability of the ligand L. A comparison of the geometry of the Mn(CNSbCl5) moiety with those of other L·SbCl5 species showed that the manganese ligand is a donor comparable with a range of other nitrogen and oxygen ligands but much weaker than ligands such as the phenyl anion. The geometry variations were analysed using a qualitative molecular orbital model for the bonding in L·SbCl5 species.

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