Issue 35, 2018

Synthesis, structures, and reactivity studies of cyclometalated N-heterocyclic carbene complexes of ruthenium

Abstract

An unusual cyclometalation reaction results from a C–C bond activation in Cp*(IPr)RuCl to give Cp*(IPr′)Ru(L) featuring a NHC-C(sp2) chelating ligand (5-L; L = propene, N2; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; IPr′ = 1-(6-isopropylphenyl)-3-(2,6-diisopropylphenyl)imidazol-2-ylidene). DFT calculations were employed to elucidate the C–C bond activation pathway. Reactions of cyclometalated ruthenium complexes bearing NHC-C(sp2) and NHC-C(sp3) ligands (5-L and Cp*(IXy-H)Ru(N2), 1a, respectively where IXy = 1,3-bis(2,6-dimethylphenyl)-imidazol-2-ylidene; IXy-H is the deprotonated form of (IXy)) are reported. Deprotonation of 1a by an equimolar mixture of benzyl potassium and 18-crown-6 afforded a doubly-cyclometalated complex [Cp*(IXy-2H)Ru][K(18-crown-6)] (7). A lower CO stretching frequency in Cp*(IXy-H)Ru(CO) (8) vs. Cp*(IPr′)Ru(CO) (9) suggests that the NHC-C(sp3) ligand is more electron donating. Complexes 5-L reacted with H2 to give the dihydride Cp*(IPr′)RuH2 (11). In comparison, after an initial oxidative addition of H2, complex 1a with its more reactive Ru–C(sp3) bond underwent C–H bond reductive elimination, and a second oxidative addition of H2 afforded the trihydride Cp*(IXy)RuH3 (10). Reaction of 1a with B(C6F5)3 resulted in a zwitterionic complex Cp*Ru(IXy′′) (12; IXy′′ = 1-[2-((C6F5)3BCH2)C6H3-6-methyl]-3-(2,6-dimethylphenyl)imidazol-2-ylidene-1-yl) by the formation of a new C–B bond. In contrast, B(C6F5)3 abstracted a hydride from 5-L and promoted a very unusual C–C bond formation involving insertion of an allyl ligand into a Ru–C bond to form [Cp*Ru(IPr′′)][HB(C6F5)3] (IPr′′ = 1-[2-(CH2[double bond, length as m-dash]CHCH2)C6H3-6-isopropyl]-3-(2,6-diisopropyl)imidazol-2-ylidene-1-yl) (13).

Graphical abstract: Synthesis, structures, and reactivity studies of cyclometalated N-heterocyclic carbene complexes of ruthenium

Supplementary files

Article information

Article type
Paper
Submitted
13 may. 2018
Accepted
06 jul. 2018
First published
27 jul. 2018

Dalton Trans., 2018,47, 12138-12146

Author version available

Synthesis, structures, and reactivity studies of cyclometalated N-heterocyclic carbene complexes of ruthenium

H. Liu, M. S. Ziegler and T. D. Tilley, Dalton Trans., 2018, 47, 12138 DOI: 10.1039/C8DT01925H

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