Bis(phosphinimino)amide Supported Borondihydride and Heteroleptic Dihalo Compounds of Group 13

The reaction of tetraphenyldiphosphazane (Ph 2 P) 2 NH with mesityl azide 2,4,6‐Me 3 C 6 H 2 ‐N 3 affords a new [ N , N′ ] chelating ligand, [HN(Ph 2 PN(2,4,6‐Me 3 C 6 H 2 )) 2 ] ( LH ). The ligand can be easily deprotonated by using n BuLi or Li[N(SiMe 3 ) 2 ] in Et 2 O to yield [{N(Ph 2 PN(2,4,6‐Me 3 C 6 H 2 )) 2 }Li · OEt 2 ] ( 1 ). The reaction of LH with AlMe 3 and BH 3 · SMe 2 , respectively, gives the corresponding mononuclear complexes [{N(Ph 2 PN(2,4,6‐Me 3 C 6 H 2 )) 2 }AlMe 2 ] ( 2 ) and a rare borondihydride [{N(Ph 2 PN(2,4,6‐Me 3 C 6 H 2 )) 2 }BH 2 ] ( 3 ). Similarly, reaction of 1 with the trihalides, MX 3 , of group 13 elements afford the corresponding dihalo complexes, [{N(Ph 2 PN(2,4,6‐Me 3 C 6 H 2 )) 2 }MX 2 ] [M = B, X = F ( 4 ); M = Al, X = Cl ( 5 ); M = Ga, X = Cl ( 6 ); M = In, X = Br ( 7 )]. All the complexes reported in this work have been isolated in good yields and are expected to serve as useful synthons in a number of reactions. The solid‐state structure of LH and 1 – 7 have been investigated by single‐crystal X‐ray structural analysis.