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Synthesis, Characterization, and Reactivity Study of a Chromium(VI) Neopentylidene Complex
Yiru Fan1, Yanhua Yu1, Qi Wang1
1Department of Chemistry, College of Science, Shanghai University, Shanghai 200444, PR China.
Abstract:
The bis(arylimido)chromium(VI) dineopentyl complex, (ArN)2Cr(CH2tBu)2 (Ar = 2,6-diisopropylphenyl), undergoes α-hydrogen abstraction to generate a coordinatively unsaturated neopentylidene intermediate, which can be trapped by a σ-donor ligand (tetramethylurea) to afford the corresponding adduct (ArN)2Cr(═CHtBu)[OC(NMe2)2]. Due to its high reactivity, the neopentylidene intermediate subsequently reacts with tBuCN to generate a tris(imido)chromium(VI) complex (ArN)2Cr[═N-C(tBu)═CHtBu](NCtBu). The N-bonded tBuCN can be replaced by a strong σ-donor PPh3, making a phosphine adduct (ArN)2Cr[═N-C(tBu)═CHtBu](PPh3). Additionally, the neopentylidene intermediate can react with tBuNCO via cycloaddition, ring-opening metathesis, and cycloaddition to yield a biuret complex (ArN)2Cr{[tBuNC(O)]2NtBu}. It also reacts with cyclohexene in a [2 + 2] cycloaddition to afford the chromacyclobutane derivative (ArN)2Cr(C11H20). In addition to cycloaddition, 1,2-addition is a typical reactivity pattern of the neopentylidene intermediate. The neopentylidene intermediate can react with dimethyl carbonate and tBuNH2 to afford complexes (ArN)2Cr(OMe)[C(COOMe)HtBu] and (ArN)2Cr(CH2tBu)(NHtBu), respectively.
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