Exploiting the Electronic Tuneability of Carboranes as Supports for Frustrated Lewis Pairs

利用碳硼烷的电子可调性作为受挫路易斯对的载体

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作者:Amanda Benton, Zachariah Copeland, Stephen M Mansell, Georgina M Rosair, Alan J Welch

Abstract

The first example of a carborane with a catecholborolyl substituent, [1-Bcat-2-Ph-closo-1,2-C&sub2;B10H10] (1), has been prepared and characterized and shown to act as the Lewis acid component of an intermolecular frustrated Lewis pair in catalyzing a Michael addition. In combination with B(C₆F₅)&sub3; the C-carboranylphosphine [1-PPh&sub2;-closo-1,2-C&sub2;B10H11] (IVa) is found to be comparable with PPh&sub2;(C₆F₅) in its ability to catalyze hydrosilylation, whilst the more strongly basic B-carboranylphosphine [9-PPh&sub2;-closo-1,7-C&sub2;B10H11] (V) is less effective and the very weakly basic species [μ-2,2'-PPh-{1-(1'-1',2'-closo-C&sub2;B10H10)-1,2-closo-C&sub2;B10H10}] (IX) is completely ineffective. Base strengths are rank-ordered via measurement of the ¹J 31P-77Se coupling constants of the phosphineselenides [1-SePPh&sub2;-closo-1,2-C&sub2;B10H11] (2), [9-SePPh&sub2;-closo-1,7-C&sub2;B10H11] (3), and [SePPh&sub2;(C₆F₅)] (4).

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