Synthesis and structural studies of rhodium complexes of phosphorus—sulfur ligands

Author:

Dick David G.,Stephan Douglas W.

Abstract

Rhodium complexes of the phosphorus—sulfur ligands, 2-diphenylphosphinoethyl methyl sulfide (MeSP), 1, and 2-diphenylphosphinothiophene (PTH), 2, have been prepared and studied by single crystal X-ray diffraction methods. [Rh(MeSP)2]BF4•H2O, 3, crystallizes in the space group P21/n with a = 16.939(6) Å, b = 17.152(5) Å, c = 12.049(9) Å, β = 106.50(4)°, and Z = 4. The MeSP ligands chelate to Rh yielding a distorted square-planar geometry. The disposition of the methyl groups on the cis sulfur atoms is transoid. Average Rh—P and Rh—S bond distances were found to be 2.225(3) and 2.347(3) Å, respectively. [Rh(PTH)2(COD)]BF4, 4, crystallizes in the space group Cc with a = 15.862(2) Å, b = 15.112(3) Å, c = 16.029(3) Å, β = 103.32(1)°, and Z = 4. The Rh atom in 4 also has essentially a square-planar coordination geometry. 2 does not chelate but rather is monohapto through phosphorus. Rh—P distances of 2.319(3) and 2.378(3) Å and Rh—C distances of 2.17(1), 2.22(1), 2.24(1), and 2.27(1) Å were found. The small variations in the Rh—P and Rh—C bonds distances appear to be a result of steric interactions between 2 and the COD ligand.

Publisher

Canadian Science Publishing

Subject

Organic Chemistry,General Chemistry,Catalysis

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