Reactivity of the rhodium(III) formamidinato-complex [Rh(η-C5Me5)Cl(p-MeC6H4N CH NC6H4Me-p)] with CO and heterocumulenes. Crystal and molecular structure of the thioureido-complex [Rh(η-C5Me5)Cl{PhN C[N(C6H4Me-p)–CHNC6H4Me-p] S}]

Abstract

The complex [Rh(η-C₅Me₅)Cl(p-MeC₆H₄N CH NC₆H₄Me-p)] reacts with CO, CS₂, and PhNCS giving respectively the carbamoyl [Rh(η-C₅Me₅)Cl{CO–N(C₆H₄Me-p)CHNC₆H₄Me-p}], dithiocarbamato-[Rh(η-C₅Me₅)Cl{S C[N(C₆H₄Me-p)–CHNC₆H₄Me-p] S}], and thioureido-complexes [Rh(η-C₅Me₅)Cl{PhN C[N(C₆H₄Me-p)–CHNC₆H₄Me-p] S}]via formal insertion into the Rh–N bond. The structure of the thioureido-complex has been determined by single-crystal X-ray diffraction: space group P with a= 9.339(2), b= 12.130(3), c= 13.950(3)Å, α= 95.7(1), β= 96.3(1), γ= 103.9(1)°, and Z= 2. Refinement on the basis of the 3 225 observed reflections [I 2σ(I)] gave a final conventional R value of 0.046 (R′= 0.046). The molecule contains the four-membered chelate ring R[graphic omitted]. The C–N and C–S bonds [1.299(8) and 1.741(6)Å] have a considerable double-bond character with a higher percentage for the former.