Synthesis and crystal structures of carbonyl derivatives of chloride–tetramethylene sulfoxide–ruthenium(III) complexes: [RuCl3(TMSO)2(CO)] and [H(TMSO)2] [RuCl4(TMSO)(CO)]

The synthesis, spectroscopic characterization and crystal structure of [RuCl3(TMSO)2(CO)] (1) and [H(TMSO)2][RuCl4(TMSO)(CO)] (2) are reported. These complexes are prepared by the reaction of the precursors [mer-RuCl3(TMSO)3] and [H(TMSO)][RuCl4(TMSO)2] with carbon monoxide in the presence or absence of TMSO at ambient temperature and pressure. Complexes 1 and 2 represents the first examples of Ru(III) compounds bearing both tetramethylene sulfoxide and carbon monoxide ligands on the metal. Substitution of one of the two trans-S-bonded TMSO from the anion accompanied addition of one molecule of TMSO on the cation. Coordination of CO induces an S-to-O linkage isomerization of the TMSO ligands. The crystal of 1 is a red–orange needle, monoclinic, space group C2/c, a=26.446(2) Å, b=8.8726(6) Å, c=15.1093(8) Å, β=107.427(4)°. The crystal of 2 is an orange needle, orthorhombic, space group Pnma, a=11.9820(9) Å, b=14.1930(11) Å, c=12.6500(15) Å.