(BB)-Carboryne Complex of Ruthenium: Synthesis by Double B–H Activation at a Single Metal Center

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• 作者：Bennett J. Eleazer ; Mark D. Smith ; Alexey A. Popov ; Dmitry V. Peryshkov
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：August 24, 2016
• 年：2016
• 卷：138
• 期：33
• 页码：10531-10538
• 全文大小：603K
• 年卷期：0
• ISSN：1520-5126

文摘

The first example of a transition metal (BB)-carboryne complex containing two boron atoms of the icosahedral cage connected to a single exohedral metal center (POBBOP)Ru(CO)₂ (POBBOP = 1,7-OP(i-Pr)₂-2,6-dehydro-m-carborane) was synthesized by double B–H activation within the strained m-carboranyl pincer framework. Theoretical calculations revealed that the unique three-membered (BB)>Ru metalacycle is formed by two bent B–Ru σ-bonds with the concomitant increase of the bond order between the two metalated boron atoms. The reactivity of the highly strained electron-rich (BB)-carboryne fragment with small molecules was probed by reactions with electrophiles. The carboryne–carboranyl transformations reported herein represent a new mode of cooperative metal–ligand reactivity of boron-based complexes.