Reactions of the cationic bis(chelate) rhodium complex [Rh(P down curve sign O)2]+ with SO2, CS2 and O2/SO2

Article abstract of DOI:10.1016/0022-328X(95)06038-X

The cationic bis(chelate) complex [Rh(P down curve sign O)₂][BPh₄] (1) (P down curve sign O: η²(O, P)-chelated (C₆H₁₁)₂PCH₂CH₂OCH₃ ligand) reacts with CS₂ and SO₂ to form the η²(C, S)-coordinated carbon disulfide complex [RhCS₂(P down curve sign O)₂][BPh₄] (2) and the square-pyramidal η¹-SO₂ complex [Rh(η¹-SO₂)(P down curve sign O)₂][BPh₄] (4) respectively. According to the IR spectra, in complex 4 the RhSO₂ fragment adopts a pyramidal geometry. Upon treatment of the η²-oxygen rhodium complex [RhO₂(P down curve sign O)₂][BPh₄] (3) with SO₂, the sulfato-O,O'-rhodium complex [RhSO₄(P down curve sign O)₂][BPh₄] (5) is accessible. The same compound is also available if complex 4 is reacted with oxygen. ¹⁰³Rh NMR investigations afford additional evidence for the coordination geometry in the complexes 1, 3, 4 and 5.