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Diverse Bonding Activations in the Reactivity of a Pentaphenylborole toward Sodium Phosphaethynolate: Heterocycle Synthesis and Mechanistic Studies
Y. Li, R.K. Siwatch, T. Mondal, Y. Li, , D. Koley, C.-W. So
Published in American Chemical Society
PMID: 28322546
Volume: 56
Issue: 7
Pages: 4112 - 4120
The reaction of the pentaphenylborole [(PhC)4BPh] (1) with sodium phosphaethynolate·1,4-dioxane (NaOCP(1,4-dioxane)1.7) afforded the novel sodium salt of phosphaboraheterocycle 2. It comprises anionic fused tetracyclic P/B-heterocycles that arise from multiple bond activation between the borole backbone and [OCP]−anion. Density functional theory calculations indicate that the [OCP]− anion prefers the form of phosphaethynolate -O-CP over phosphaketenide OCP- to interact with two molecules of 1, along with various B-C, C-P, and C-C bond activations to form 2. The calculations were verified by experimental studies: (i) the reaction of 1 with NaOCP(1,4-dioxane)1.7 and a Lewis base such as the N-heterocyclic carbene IAr [:C{N(Ar)CH}2] (Ar = 2,6-iPr2C6H3) and amidinato amidosilylene [{PhC(NtBu)2}(Me2N)Si:] afforded the Lewis base-pentaphenylborole adducts [(PhC)4B(Ph)(LB)] (LB = IAr (3), :Si(NMe2){(NtBu)2CPh} (4)), respectively; (ii) the reaction of 1 with the carbodiimide ArNCNAr afforded the seven-membered B/N heterocycle [B(Ph) (CPh)4C(NAr)N(Ar)] (5). Compounds 2-5 were fully characterized by NMR spectroscopy and X-ray crystallography. © 2017 American Chemical Society.
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