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Published on: March 24, 2018
Monomeric Two-coordinate Beryllium Imido and Boryloxide Complexes Featuring Be-N and Be-O Triple Bonds
Christoph Helling1, David J D Wilson2, Cameron Jones1
1School of Chemistry, Monash University, PO Box 23, Melbourne, VIC 3800, Australia.
Abstract:
The 2p elements possess a unique propensity to participate in multiple bonding. Realization of multiple bonding involving the 2s elements, however, is challenging and remains exceedingly rare. In this contribution, we present the syntheses, detailed characterization, and molecular structures of heteroleptic beryllium imido and boryloxide complexes of the type [(HCNDip)2YXBeAr(OEt2)] (Y,X = C,N or B,O; n = 0, 1; m = 1, 2; Dip = 2,6-iPr2C6H3) by salt metathesis and arene elimination approaches. Systematic adjustment of the steric demand of the aryl substituent resulted in the isolation of monomeric, two-coordinate beryllium imido and boryloxide complexes, (HCNDip)2CNBeTip (9, Tip = 2,4,6-iPr3C6H2) and (HCNDip)2BOBeArDip (12, ArDip = 2,6-Dip2C6H3), containing virtually linear C-N-Be-C and B-O-Be-C arrangements and extremely short Be-N (1.434(2) Å, 1.437(3) Å) and Be-O (1.4035(14) Å) bonds, respectively. These were shown by in-depth computational electronic structure and bonding analyses to possess unprecedented triple bond character. The Be-O bond in 12 constitutes the first s-block metal-oxygen multiple bond.
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