A 113Cd nuclear magnetic resonance study of some complexes of cadmium with phosphine oxides, sulfides, and selenides

Abstract

113Cd(AsF6)2 has been synthesized from 113CdO by treatment in SO2 with PF5 then AsF5. From the 113Cd-enriched salt have been prepared [Cd(EPR3)4]2+ (E = O, R = C6H11; E = S or Se, R = Ph), [Cd(SP(C6H11)3)x(SeP(C6H11)n−x]2+ (n = 4, x = 0–4; n = 3, x = 0–3), [Cd(EP(o-C6H4Me)3)n]2+ (E = S, n = 4 or 2; E = Se, n = 3 or 2), [Cd(Ph2P(O)(CH2)nP(O)Ph2)3]2+ (n = 1 or 2), and [Cd(Ph2P(O)((CH2)2P(O)Ph2)2)2]2+ in liquid SO2. The reduced temperature slow exchange 31P and 113Cd nmr spectra have been measured and are discussed. The 31P nmr are as expected from previous work on complexes containing 113Cd at natural abundance except that several values of 2J(113Cd—O—31P) have been measured. From the 113Cd spectra the most important shielding sequences observed are [Formula: see text] for [Cd(EP(C6H11)3)4]2+, δ2:1 < δ3:1 < δ4:1 for [Cd(EPR3)n]2+ (E = S or Se, n = 1–4, constant R), and [Formula: see text] for the various phosphine oxide complexes studied.The synthesis of SO2-insoluble Cd(SbF6)2•3(OP(C6H11)3) is reported.