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Issue 7, 2018
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Metal alkyls programmed to generate metal alkylidenes by α-H abstraction: prognosis from NMR chemical shift

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Abstract

Metal alkylidenes, which are key organometallic intermediates in reactions such as olefination or alkene and alkane metathesis, are typically generated from metal dialkyl compounds [M](CH2R)2 that show distinctively deshielded chemical shifts for their α-carbons. Experimental solid-state NMR measurements combined with DFT/ZORA calculations and a chemical shift tensor analysis reveal that this remarkable deshielding originates from an empty metal d-orbital oriented in the M–Cα–Cα′ plane, interacting with the Cα p-orbital lying in the same plane. This π-type interaction inscribes some alkylidene character into Cα that favors alkylidene generation via α-H abstraction. The extent of the deshielding and the anisotropy of the alkyl chemical shift tensors distinguishes [M](CH2R)2 compounds that form alkylidenes from those that do not, relating the reactivity to molecular orbitals of the respective molecules. The α-carbon chemical shifts and tensor orientations thus predict the reactivity of metal alkyl compounds towards alkylidene generation.

Graphical abstract: Metal alkyls programmed to generate metal alkylidenes by α-H abstraction: prognosis from NMR chemical shift

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Supplementary files

Article information


Submitted
24 Nov 2017
Accepted
04 Jan 2018
First published
05 Jan 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, 1912-1918
Article type
Edge Article

Metal alkyls programmed to generate metal alkylidenes by α-H abstraction: prognosis from NMR chemical shift

C. P. Gordon, K. Yamamoto, K. Searles, S. Shirase, R. A. Andersen, O. Eisenstein and C. Copéret, Chem. Sci., 2018, 9, 1912
DOI: 10.1039/C7SC05039A

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