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Issue 5, 2021

Reversible carbon–boron bond formation at platinum centers through σ-BH complexes

Author affiliations

Abstract

A reversible carbon–boron bond formation has been observed in the reaction of the coordinatively unsaturated, cyclometalated, Pt(II) complex [Pt(ItBuiPr′)(ItBuiPr)][BArF], 1, with tricoordinated boranes HBR2. X-ray diffraction studies provided structural snapshots of the sequence of reactions involved in the process. At low temperature, we observed the initial formation of the unprecedented σ-BH complexes [Pt(HBR2)(ItBuiPr′)(ItBuiPr)][BArF], one of which has been isolated. From −15 to +10 °C, the σ-BH species undergo a carbon–boron coupling process leading to the platinum hydride derivative [Pt(H)(ItBuiPr–BR2)(ItBuiPr)][BArF], 4. Surprisingly, these compounds are thermally unstable undergoing carbon–boron bond cleavage at room temperature that results in the 14-electron Pt(II) boryl species [Pt(BR2)(ItBuiPr)2][BArF], 2. This unusual reaction process has been corroborated by computational methods, which indicate that the carbon–boron coupling products 4 are formed under kinetic control whereas the platinum boryl species 2, arising from competitive C–H bond coupling, are thermodynamically more stable. These findings provide valuable information about the factors governing productive carbon–boron coupling reactions at transition metal centers.

Graphical abstract: Reversible carbon–boron bond formation at platinum centers through σ-BH complexes

Supplementary files

Article information


Submitted
06 Oct 2020
Accepted
09 Nov 2020
First published
10 Nov 2020

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

Chem. Sci., 2021,12, 1647-1655
Article type
Edge Article

Reversible carbon–boron bond formation at platinum centers through σ-BH complexes

P. Ríos, R. Martín-de la Calle, P. Vidossich, F. J. Fernández-de-Córdova, A. Lledós and S. Conejero, Chem. Sci., 2021, 12, 1647 DOI: 10.1039/D0SC05522K

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