Crystallographic and Dynamic NMR Evidence for Organometallic Fragments Pivoting on a Molecular Oxide Surface

Abstract

A new vanadate-supported organorhodium complex, [{(η4-C6H10)Rh}2(V4O12)]2-, was synthesized. Multinuclear dynamic NMR experiments revealed that the organorhodium fragments pivot on the surface of V4O12. The X-ray crystal structural study of [{C6H5)3P}2N]2[{(η4-C6H10)Rh}2(V4O12)]·2C4H4Cl2 (monoclinic, space group P21/n, a = 18.075(2) Å, b = 17.965(2) Å, c = 28.117(2) Å, β = 102.20(1)°, V = 8924(2) Å3, Z = 4) reveals that the complex anion assumes an endo form in the solid state, while a closely related complex [{(η4-C8H14)Rh}2(V4O12)]2- has been reported to assume an exo form in the crystalline state.