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Issue 9, 2018
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Expansion of the (BB)[double bond splayed left]Ru metallacycle with coinage metal cations: formation of B–M–Ru–B (M = Cu, Ag, Au) dimetalacyclodiboryls

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Abstract

In this work, we introduce a novel approach for the selective assembly of heterometallic complexes by unprecedented coordination of coinage metal cations to strained single ruthenium–boron bonds on a surface of icosahedral boron clusters. M(I) cations (M = Cu, Ag, and Au) insert into B–Ru bonds of the (BB)–carboryne complex of ruthenium with the formation of four-membered B–M–Ru–B metalacycles. Results of theoretical calculations suggest that bonding within these metalacycles can be best described as unusual three-center-two-electron B–M⋯Ru interactions that are isolobal to B–H⋯Ru borane coordination for M = Cu and Ag, or the pairs of two-center-two electron B–Au and Au–Ru interactions for M = Au. These transformations comprise the first synthetic route to exohedral coinage metal boryl complexes of icosahedral closo-{C2B10} clusters, which feature short Cu–B (2.029(2) Å) and Ag–B (2.182(3) Å) bonds and the shortest Au–B bond (2.027(2) Å) reported to date. The reported heterometallic complexes contain Cu(I) and Au(I) centers in uncharacteristic square-planar coordination environments. These findings pave the way to rational construction of a broader class of multimetallic architectures featuring M–B bonds.

Graphical abstract: Expansion of the (BB) [[double bond splayed left]] Ru metallacycle with coinage metal cations: formation of B–M–Ru–B (M = Cu, Ag, Au) dimetalacyclodiboryls

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Article information


Submitted
12 Jan 2018
Accepted
03 Feb 2018
First published
05 Feb 2018

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2018,9, 2601-2608
Article type
Edge Article

Expansion of the (BB)[double bond splayed left]Ru metallacycle with coinage metal cations: formation of B–M–Ru–B (M = Cu, Ag, Au) dimetalacyclodiboryls

B. J. Eleazer, M. D. Smith, A. A. Popov and D. V. Peryshkov, Chem. Sci., 2018, 9, 2601
DOI: 10.1039/C8SC00190A

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