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

Bennett J. Eleazer | Zendy; Mark D. Smith | Zendy; Alexey A. Popov | Zendy; Dmitry V. Peryshkov | Zendy

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

Author(s) -

Bennett J. Eleazer,

Mark D. Smith,

Alexey A. Popov,

Dmitry V. Peryshkov

Publication year - 2016

Publication title -

journal of the american chemical society

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 7.115

H-Index - 612

eISSN - 1520-5126

pISSN - 0002-7863

DOI - 10.1021/jacs.6b05172

Subject(s) - chemistry , ruthenium , carborane , pincer movement , reactivity (psychology) , boron , icosahedral symmetry , electrophile , metal , crystallography , transition metal , ligand (biochemistry) , molecule , main group element , stereochemistry , catalysis , organic chemistry , medicine , biochemistry , alternative medicine , receptor , pathology

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.

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