Acetylacetonatobis(isocyanide)(tetracyanoethylene)rhodium and related complexes. Rotation of tetracyanoethylene

Add time:07/30/2019    Source:sciencedirect.com

Two types of square-planar rhodium(I) isocyanide complexes, Rh(acac)(RNC)2 (acac = CH3COCHC OCH3−; R = t-Bu, p-CH3OC6H4, p-CH3C6H4, p-ClC6H4, 2,4,6-(CH3)3C6H2) and Rh(acac)(R′ NC) (PPh3) (R′ = p-CH3OC6H4, p-CH3C6H4, p-ClC6H4), have been synthesized. They react with tetracyanoethylene (TCNE) to give the 1:1 adducts, Rh(acac) (RNC)2(TCNE) and Rh(acac)(R′ NC)(PPh3)(TCNE). Configurational behaviors of these complexes in solution are described from ir and pmr spectra. Rh(acac) (RNC)2(TCNE) gives temperature-dependent pmr spectra which are interpreted in terms of the TCNE rotation around the rhodium-TCNE bond accompanying Berry pseudorotation in a trigonal bipyramid.

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