Issue 13, 2020

Sterically controlled reductive oligomerisations of CO by activated magnesium(i) compounds: deltate vs. ethenediolate formation

Abstract

An extremely bulky, symmetrical three-coordinate magnesium(I) complex, [{(TCHPNacnac)Mg}2] (TCHPNacnac = [{(TCHP)NCMe}2CH], TCHP = 2,4,6-tricyclohexylphenyl) has been prepared and shown to have an extremely long Mg–Mg bond (3.021(1) Å) for such a complex. It was shown not to react with either DMAP (4-dimethylaminopyridine) or CO. Three unsymmetrical 1 : 1 DMAP adducts of less bulky Mg–Mg bonded species have been prepared, viz. [(ArNacnac)Mg–Mg(DMAP)(ArNacnac)] (ArNacnac = [(ArNCMe)2CH] Ar = 2,6-xylyl (Xyl), mesityl (Mes) or 2,6-diethylphenyl (Dep)), and their reactivity toward CO explored. Like the previously reported bulkier complex, [(DipNacnac)Mg–Mg(DMAP)(DipNacnac)] (Dip = 2,6-diisopropylphenyl), [(DepNacnac)Mg–Mg(DMAP)(DepNacnac)] reductively trimerises CO to give a rare example of a deltate complex, [{(DepNacnac)Mg(μ-C3O3)Mg(DMAP)(DepNacnac)}2]. In contrast, the two smaller adduct complexes react with only two CO molecules, ultimately giving unusual ethenediolate complexes [{(ArNacnac)Mg{μ-OC(H)[double bond, length as m-dash]C(DMAP−H)O}Mg(ArNacnac)}2] (Ar = Xyl or Mes). DFT calculations show the latter reactions to proceed via reductive dimerizations of CO, and subsequent intramolecular C–H activation of Mg-ligated DMAP by “zig–zag” [C2O2]2− fragments of reaction intermediates. Calculations also suggest that magnesium deltate complexes are kinetic products in these reactions, while the magnesium ethenediolates are thermodynamic products. This study shows that subtle changes to the bulk of the reacting 1 : 1 DMAP–magnesium(I) adduct complexes can lead to fine steric control over the products arising from their CO reductive oligomerisations. Furthermore, it is found that the more activated nature of the adduct complexes, relative to their symmetrical, three-coordinate counterparts, [{(ArNacnac)Mg}2], likely derives more from the polarisation of the Mg–Mg bonds of the former, than the elongated nature of those bonds.

Graphical abstract: Sterically controlled reductive oligomerisations of CO by activated magnesium(i) compounds: deltate vs. ethenediolate formation

Supplementary files

Article information

Article type
Edge Article
Submitted
12 Febr. 2020
Accepted
03 Marts 2020
First published
06 Marts 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2020,11, 3516-3522

Sterically controlled reductive oligomerisations of CO by activated magnesium(I) compounds: deltate vs. ethenediolate formation

K. Yuvaraj, I. Douair, D. D. L. Jones, L. Maron and C. Jones, Chem. Sci., 2020, 11, 3516 DOI: 10.1039/D0SC00836B

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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