Zinc Dihydride and Mixed Halo Hydrides Supported by an N‐Heterocyclic Carbene

A series of zinc dihalides [(IMes)ZnX 2 ] [X = Cl ( 1a ) Br ( 1b ), I ( 1c ); IMes = 1,3‐bis(2,4,6‐trimethylphenyl)imidazolin‐2‐ylidene] is reported. The iodide 1c underwent salt metathesis with NaH as an alternative synthesis of [(IMes)ZnH 2 ] 2 ( 2 ). 2 readily reacted with ( t Bu)NCO and Ph 2 CO under Zn‐H insertion to give [(IMes)Zn( t BuNCHO‐κN) 2 ] ( 3 ) and [(IMes)Zn(OCHPh 2 ) 2 ] ( 4 ), respectively. Ph 2 S 2 and I 2 oxidized the hydride ligands in 2 to give dihydrogen and [(IMes)Zn(SPh) 2 ] ( 5 ) and 1c , respectively. A series of mixed halo hydrides [(IMes)Zn(X)(H)] 2 [X = Cl ( 6a ), Br ( 6b ), I ( 6c )] was obtained upon comproportionating 2 with 1a – c . The new compounds were fully characterized, including X‐ray crystallographic analysis of 3 and 6b .