The synthesis and nuclear magnetic resonance spectroscopic study of [Rh10S(CO)22]2–

Abstract

The reaction of [Rh₄(CO)₁₂] with SCN^– in PrⁱOH or tetrahydrofuran at atmospheric pressure gives [Rh₁₀S(CO)₂₂]^2– in good yield. The reaction is complex and the nature of some of the reaction intermediates is discussed. N.m.r. spectroscopic studies (¹⁰³Rh, ¹³C, and ¹³C-{¹⁰³Rh}) at low temperature show the solution structure of [Rh₁₀S(CO)₂₂]^2– to be entirely consistent with that found in the solid state; at higher temperatures complete fluxionality of both the carbonyl and metal polyhedra is found. At 95 °C, conversion into [Rh₁₇(S)₂(CO)₃₂]^3– occurs.