Hydride Transfer Reactivity of Mo(L)(H)(depe) 2 (L = N, NBEt 3 )

Starting from Mo(N 2 ) 2 (depe) 2 ( 1 ), the nitrido complex Mo(N)(N 3 )(depe) 2 ( 2 ) was obtained by the reaction of 1 with Me 3 SiN 3 . Subsequent reaction of 2 with HCl in CH 3 OH afforded the cationic imido chloride 3 , which could be converted into the nitrido chloride 4 with sodium bis(trimethylsilyl)amide. From 3 and 4 the hydrido complexes of the type Mo(H)(L)(depe) 2 [L = N ( 7 ), NBEt 3 ( 8 )] were obtained by the reaction with the hydride reagents LiBH 4 and NaHBEt 3 . The hydridic character of the L n M–H bond of 8 was determined by DQCC measurements (bond ionicity i = 81 %). Hydride reactivity studies were carried out on 7 and 8 ; however, only 8 underwent hydride transfer reactions. 8 reacted with 4,4′‐dichlorobenzophenone and acetophenone to afford the corresponding alkoxide complexes Mo(NBEt 3 )(OCHRR′)(depe) 2 [R, R′ = C 6 H 4 Cl ( 10 ); R = Me, R′ = Ph ( 11 )]. The high propensity of 8 to undergo carbonyl insertion was documented further by reactions with CO 2 and carbonylmetal compounds. Conversion with CO 2 led to formation of the formato complex Mo(NBEt 3 )(OCHO)(depe) 2 ( 9 ) and reactions with Fe(CO) 5 and Re 2 (CO) 10 resulted in the formation of Mo[(μ‐OCH)Fe(CO) 4 ](NBEt 3 )(depe) 2 ( 12 ) and Mo[(μ‐OCH)Re 2 (CO) 9 ](NBEt 3 )(depe) 2 ( 13 ). X‐ray diffraction studies were carried out on 1 – 4 , 6 , 8 – 10 and 12 – 14 . (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)