109889-91-0Relevant academic research and scientific papers
Synthesis and structure of ReO(PMe3)(CH2SiMe3)3 and reaction with carbon monoxide
Cai, Shiang,Hoffman, David M.,Lappas, Dimitrios,Woo, Hee-Gweon,Huffman, John C.
, p. 2273 - 2278 (1987)
The reactive d2 square-pyramidal complex ReO(PMe3) (CH2SiMe3)3 has been prepared by the addition of 3 equiv of Me3SiCH2MgCl to ReO(OEt)Cl2(py)2 in the presence of PMe3 (63% yield) and by the reaction of an excess of PMe3 with Re2O3(CH2SiMe3)6 (86% yield). The complex ReO(PMe3)(CH2SiMe3)3 reacts rapidly in pentane with CO to give purple ReO(PMe3)(η2-C(O)CH2SiMe 3)(CH2SiMe3)2 in 86% yield. An analogous pyridine complex, ReO(py)(η2-C(O)CH2SiMe3)(CH 2SiMe3)2, is prepared by adding CO to an equilibrium mixture of Re2O3(CH2SiMe3)6 + py = ReO(py)(CH2SiMe3)3 + ReO2(CH2SiMe3)3. The complex Re2O3(CH2SiMe3)6 also reacts with O2, DMSO, or pyridine N-oxide to yield the yellow oil ReO2(CH2SiMe3)3, which is proposed to have a trigonal-bipyramidal geometry with the oxo ligands in the equatorial plane. Photolysis of ReO2(CH2SiMe3)3 in hydrocarbon solvents gives the d1-d1 dimer Re2O4(CH2SiMe3)4 as a dark yellow oil. Crystal data for ReO(PMe3)(CH2SiMe3)3 at -161°C: a = 12.090 (3) A?, b = 20.288 (7) A?, c = 19.950 (6) A?, Z = 8, dcalcd = 1.466 g cm-3, and space group Pbca.
