Issue 3, 2018

Mono- and dinuclear Ni(i) products formed upon bromide abstraction from the Ni(i) ring-expanded NHC complex [Ni(6-Mes)(PPh3)Br]

Abstract

Bromide abstraction from the three-coordinate Ni(I) ring-expanded N-heterocyclic carbene complex [Ni(6-Mes)(PPh3)Br] (1; 6-Mes = 1,3-bis(2,4,6-trimethylphenyl)-3,4,5,6-tetrahydropyrimidin-2-ylidene) with TlPF6 in THF yields the T-shaped cationic solvent complex, [Ni(6-Mes)(PPh3)(THF)][PF6] (2), whereas treatment with NaBArF4 in Et2O affords the dimeric Ni(I) product, [{Ni(6-Mes)(PPh3)}2(μ-Br)][BArF4] (3). Both 2 and 3 act as latent sources of the cation [Ni(6-Mes)(PPh3)]+, which can be trapped by CO to give [Ni(6-Mes)(PPh3)(CO)]+ (5). Addition of [(Et3Si)2(μ-H)][B(C6F5)4] to 1 followed by work up in toluene results in the elimination of phosphine as well as halide to afford a co-crystallised mixture of [Ni(6-Mes)(η2-C6H5Me)][B(C6F5)4] (4), and [6MesH⋯C6H5Me][B(C6F5)4]. Treatment of 1 with sodium salts of more strongly coordinating anions leads to substitution products. Thus, NaBH4 yields the neutral, diamagnetic dimer [{Ni(6-Mes)}2(BH4)2] (6), whereas NaBH3(CN) gives the paramagnetic monomeric cyanotrihydroborate complex [Ni(6-Mes)(PPh3)(NCBH3)] (7). Treatment of 1 with NaOtBu/NHPh2 affords the three-coordinate Ni(I) amido species, [Ni(6-Mes)(PPh3)(NPh2)] (8). The electronic structures of 2, 5, 7 and 8 have been analysed in comparison to that of previously reported 1 using a combination of EPR spectroscopy and density functional theory.

Graphical abstract: Mono- and dinuclear Ni(i) products formed upon bromide abstraction from the Ni(i) ring-expanded NHC complex [Ni(6-Mes)(PPh3)Br]

Supplementary files

Article information

Article type
Paper
Submitted
06 Nov. 2017
Accepted
01 Dec. 2017
First published
05 Dec. 2017
This article is Open Access
Creative Commons BY license

Dalton Trans., 2018,47, 769-782

Mono- and dinuclear Ni(I) products formed upon bromide abstraction from the Ni(I) ring-expanded NHC complex [Ni(6-Mes)(PPh3)Br]

W. J. M. Blackaby, S. Sabater, R. C. Poulten, M. J. Page, A. Folli, V. Krewald, M. F. Mahon, D. M. Murphy, E. Richards and M. K. Whittlesey, Dalton Trans., 2018, 47, 769 DOI: 10.1039/C7DT04187J

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