Rhodium complexes of Group 4B ligands
- 1 January 1975
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 23,p. 2622-2627
- https://doi.org/10.1039/dt9750002622
Abstract
The reactions of the hydrides MMe3H (M = Si, Ge, or Sn) with [Rh(η-C5H5)(CO)2] have been investigated under both photochemical and thermal conditions. The complex [Rh(η-C5H5)(CO)(GeMe3)2] is formed in highest yield (ca. 50%) photochemically and [Rh(η-C5H5)(CO)(SnMe3)2](ca. 80%) thermally (80 °C). Under u.v. irradiation, SnMe3H and [Rh(η-C5H5)(CO)2] afford [Rh(CO)3(SnMe3)3] principally (ca. 30%), whose reactions with PPh3, P(OMe)3, and cyclopentadiene have been studied. The complex [Rh(η-C5H5)(CO)(SiMe3)2] is formed in only trace amounts by either method. Reduction of [Rh(η-C5H5)(CO)2] or [Rh(η-C5H5)(CO)I2] with sodium amalgam gives an air-sensitive solution with properties characteristic of [Rh(η-C5H5)(CO)H]–. Addition of MMe3X (M = Ge, Sn, or Pb; X = halide) gives [Rh(η-C5H5)(CO)(MMe3)2](M = Ge or Sn) in fair (20–50%) yield, and [Rh(η-C5H5)(CO)(PbMe3)2] in trace amounts. Iodine smoothly cleaves [Rh(η-C5H5)(CO)(GeMe3)2] to afford [Rh(η-C5H5)(CO)(GeMe3)I], whose chemistry is described. The complex [Rh2(η-C5H5)2(CO)3] is formed in 32% yield on irradiation of [Rh(η-C5H5)(CO)2], and its reactions with MMe3H (M = Si, Ge or Sn) and P(OMe)3 have been investigated.Keywords
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