N-heterocyclic carbenes as bridgehead donors in metal pincer complexes

He, Fengkai; Zois, Konstantinos P.; Tzeli, Demeter; Danopoulos, Andreas A.; Braunstein, Pierre

doi:10.1016/j.ccr.2024.215757

Coordination Chemistry Reviews

2024

DOI: 10.1016/j.ccr.2024.215757

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N-heterocyclic carbenes as bridgehead donors in metal pincer complexes

Fengkai He,

Konstantinos P. Zois,

Demeter Tzeli

et al.

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Cited by 4 publications

References 353 publications

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New Pyridine Dicarbene Pincer Ligands with Ring Expanded NHCs and their Nickel and Chromium Complexes

Papangelis,

Pelzer,

Gourlaouen

et al. 2024

Chemistry An Asian Journal

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The pincer complexes [NiIIBr(CNC)]Br (4), [CrIIIBr3(CNC)] (5a) and [CrIIIBr2.3Cl0.7(CNC)] (5b), where CNC = 3,3'‐(pyridine‐2,6‐diyl)bis(1‐mesityl‐3,4,5,6‐tetrahydropyrimidin‐2‐ylidene), were obtained from the novel ligand CNC, generated in situ from the precursor (CHNCH)Br2 and [NiIIBr2(PPh3)2] or from [CrII{N(SiMe3)2}2(THF)2] and (CHNCH)Br2 by aminolysis, respectively. The tetrahedrally distorted square planar (τ4 ≅ 0.30) geometry and the singlet ground state of Ni in 4 were attributed to steric constraints of the CNC backbone. Computational methods highlighted the dependence of the coordination geometry and the singlet‐triplet energy difference on the size of the N‐substituent of the tetrahydropyrimidine wingtips and contrasted it to the situation in 5‐membered imidazolin‐2‐ylidene pincer analogues. The octahedral CrIII metal center in 5a and 5b is presumably formed after one electron oxidation from CH2Cl2. 4/MAO and 5a/MAO were catalysts of moderate activity for the oligomerization and polymerization of ethylene, respectively. The analogous (CH^N^CH)Br2 precursor, where (CH^N^CH) = 3,3'‐(pyridine‐2,6‐diylbis(methylene))bis(1‐mesityl‐3,4,5,6‐tetrahydropyrimidin‐1‐ium), was also prepared, however its coordination chemistry was not studied due to the inherent instability of the resulting free C^N^C ligand.

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New Pyridine Dicarbene Pincer Ligands with Ring Expanded NHCs and their Nickel and Chromium Complexes

Papangelis,

Pelzer,

Gourlaouen

et al. 2024

Chemistry An Asian Journal

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Slowing the reactivity of dicyclometalated Pd(II) complexes through the 2,6-bis(N-heterocyclic carbene)pyridine (C^N^C) non-leaving ligands: kinetic and computational study

Onunga,

Jaganyi,

Mambanda

2024

Transit Met Chem

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Air-stable palladium N Heterocyclic carbene based CCC NHC pincer complexes: Synthesis, characterization, photophysical and Raman vibrational studies, and DFT studies, plus observation of an abnormal carbene pincer

Denny,

Lang,

Autry

et al. 2025

Journal of Organometallic Chemistry

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N-heterocyclic carbenes as bridgehead donors in metal pincer complexes

Cited by 4 publications

References 353 publications

New Pyridine Dicarbene Pincer Ligands with Ring Expanded NHCs and their Nickel and Chromium Complexes

New Pyridine Dicarbene Pincer Ligands with Ring Expanded NHCs and their Nickel and Chromium Complexes

Slowing the reactivity of dicyclometalated Pd(II) complexes through the 2,6-bis(N-heterocyclic carbene)pyridine (C^N^C) non-leaving ligands: kinetic and computational study

Air-stable palladium N Heterocyclic carbene based CCC NHC pincer complexes: Synthesis, characterization, photophysical and Raman vibrational studies, and DFT studies, plus observation of an abnormal carbene pincer

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