SCHWEFEL(IV)-VERBINDUNGEN ALS LIGANDEN. III. STRUKTUR- UND BINDUNDSISOMERIE BEI ELEKTRONENREICHEN SCHWEFELDIOXIDKOMPLEXEN

Article abstract of DOI:10.1016/S0022-328X(00)99203-9

The synthesis of electron rich sulfur dioxide complexes of the types fac-M(CO)3(dmpe)(η²-SO2), mer-M(CO)3(dmpe)(η¹-SO2), mer,trans-M(CO)3(PR3)2(η¹-SO2) (M=Cr, Mo, W; PR3=PPh2Me, P(OMe)3, P(O-i-Pr)3), trans-Mo(CO)2(dppe)(PR3)(η¹-SO2) (PR3=PMe3, PPh2Me, P-i-Pr3), as well as fac-Cr(CO)3(bipy)(η²-SO2), and fac-Mo(CO)3(MeCN)2(η²-SO2) is described.The structures of these compounds are derived on the basis of NMR and vibrational spectroscopy.The results allow for an analysis of the various factors which contribute to the stability of the η¹ and η² bonding modes in (MSO2)⁶ complexes.In the tricarbonyl series SO2 can be replaced by pyridine in a reaction which in certain cases is accompanied by a change of stereochemistry around the metal.