Synthesis of carboxylate derivatives of molybdenum and tungsten based on joint insertion of CO2 and PhNCS or N, N′-dicyclohexylcarbodiimide into M-Cl bonds

Abstract

Reactions of the higher molybdenum and tungsten chlorides with phenyl isothiocyanate or with N, N′-dicyclohexylcarbodiimide and carbon dioxide in dichloroethane are the first to demonstrate the possibility of insertion of carbon dioxide in combination with other heterocumulenes into transition metal-halogen bonds. IR spectroscopy and elemental analysis data show that the reactions result in the attachment of the ligands at the same metal-chlorine bond and the formation of heteromolecular insertion products with the compositions $$\left[ {MoOCl_3 \left\{ {N\left( {Ph} \right)C\left( S \right)} \right\}_2 Nc\left( {Me} \right)Cl} \right]$$ and $$MCl_x \left\{ {OC\left( O \right)\left[ {\left( {Hex} \right)NCN\left( {Hex} \right)} \right]_2 } \right\}Cl,$$ where x = 4 and 5 for the Mo and W derivatives, respectively.