Preparation and Reactivity Studies of Four and Five coordinated Amidinate Aluminum Compounds

Synthesis of four and five coordinated aluminum amidinate (PhC(N t Bu) 2 =L) compounds are reported herein along with their single‐crystal X‐ray structures and detailed characterizations using both, experimental and computational techniques. LAlCl 2 ( 1 ) and L 2 AlCl ( 2 ) were synthesized by treating AlCl 3 with PhC(N t Bu) 2 Li in an equivalent ratio of 1 : 1 and 1 : 2, respectively. [LAl(C 2 H 5 )Cl] ( 3 ) was prepared from a reaction of AlCl 2 (C 2 H 5 ) with PhC(N t Bu) 2 Li in an equivalent ratio of 1 : 1. Reactivity of 3 , an amidinate based organo‐aluminum compound is explored for the various reactions. 3 produced [LAl(C 2 H 5 )(μ‐F)] 2 ( 4 ) on treatment with Me 3 SnF. Interestingly, [LAl(C 2 H 5 )Cl] ( 3 ) was converted to [LAlCl(μ‐OEt)] 2 ( 5 ) when refluxed in Et 2 O. 3 gives the monomeric and neutral cyclic (alkyl)(amino) carbene (cAAC) based radical [LAl(C 2 H 5 )(cAAC)] ( 6 ) on reduction with KC 8 in the presence of cAAC.