Transmethylation of a four-coordinate nickel(<scp>i</scp>) monocarbonyl species with methyl iodide

Yoo, Changho; Oh, Seohee; Jin, Kim Hyung; Lee, Yunho

doi:10.1039/c4sc01089b

Cited by 57 publications

(108 citation statements)

References 52 publications

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“…The {Ni(CO)(PNP)} − core exhibits strongly distorted tetrahedral nickel coordination ( τ 4 =0.64), resembling the anionic carbonyl pincer complex reported by Lee and co‐workers ( τ 4 =0.70) . In contrast, our nickel(I) complex [Ni(CO)(PNP)] features much weaker distortion ( τ 4 =0.24) from square‐planar geometry as compared with related nickel(I) PNP carbonyl complexes ( τ 4 =0.37–0.50) . Addition of 2 equiv [HNEt 3 ][BArF] to 7 − generated in situ (from 5 + and KC 8 ) results in immediate consumption of the carbonyl complex and formation of parent hydride 1 as main product in around 50 % spectroscopic yield besides other unidentified species (Supporting Information, Figure S22).…”

Section: Methodssupporting

confidence: 70%

Photochemically Driven Reverse Water‐Gas Shift at Ambient Conditions mediated by a Nickel Pincer Complex

et al. 2018

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The endothermic reverse water‐gas shift reaction (rWGS) for direct CO2 hydrogenation to CO is an attractive approach to carbon utilization. However, direct CO2 hydrogenation with molecular catalysts generally gives formic acid instead of CO as a result of the selectivity of CO2 insertion into M−H bonds. Based on the photochemical inversion of this selectivity, several synthetic pathways are presented for CO selective CO2 reduction with a nickel pincer platform including the first example of a photodriven rWGS cycle at ambient conditions.

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Section: Methodssupporting

confidence: 70%

Photochemically Driven Reverse Water‐Gas Shift at Ambient Conditions mediated by a Nickel Pincer Complex

et al. 2018

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“…The DFT calculations with Mulliken population analysis carried out on 3 suggests the approximately 73 % of the unpaired spin is located on Ni (Figure c). Thus, a T‐shaped Ni I center has a half‐filled

d_{x^{2} - y^{2}}

orbital as the singly occupied molecular orbital (SOMO) . This makes the addition of a fourth ligand energetically difficult due to the σ‐antibonding character of the SOMO.…”

Section: Methodsmentioning

confidence: 99%

A T‐Shaped Nickel(I) Metalloradical Species

Yoo

Lee

2017

Angewandte Chemie

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A T‐shaped NiI complex was synthesized using a rigid acridane‐based pincer ligand to prepare a metalloradical center. Structural data displays a nickel ion is embedded in the plane of a PNP ligand. Having a sterically exposed half‐filled dx2-y2 orbital, this three‐coordinate NiI species reveals unique open‐shell reactivity including the homolytic cleavage of various σ‐bonds, such as H−H, N−N, and C−C.

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“…Mononuclear square-planar Ni(II) complexes stabilized by bi-or tridentate ligands 100 A tetradentate trianionic ligand has been used by G.-H. Lee and collaborators in order to build up a model for the Methyl CoMreductase, which displays an unusual pentacoordinate environment for the metal in the +3 oxidation state (Scheme 16a). 103 The relevance of Ni(III) carbyl species supported by amido-pyridine N,N,N,N ligands in cross coupling reactions has also been established. 104 Great efforts have been made in developing Ni catalysts for alkene polymerization, particularly for the production of highly branched polyolefin structures.…”

Section: Groupmentioning

confidence: 99%

Methyl Complexes of the Transition Metals

Campos

López‐Serrano

Peloso

et al. 2016

Chemistry A European J

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Organometallic chemistry can be considered as a wide area of knowledge that combines concepts of classic organic chemistry, i.e. based essentially on carbon, with molecular inorganic chemistry, especially with coordination compounds. Transition metal methyl complexes probably represent the simplest and most fundamental way to view how these two major areas of chemistry combine and merge into novel species with intriguing features in terms of reactivity, structure, and bonding. Citing more than 500 bibliographic references, this review aims to offer a concise view of recent advances in the field of transition metal complexes containing M-CH3 fragments. Taking into account the impressive amount of data that are continuously provided by organometallic chemists in this area, this review is mainly focused on results of the last 5 years. After a panoramic overview on M-CH3 compounds of groups 3 to 11 which includes the most recent landmark findings in this area, two further sections are dedicated to methyl-bridged complexes and reactivity.

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Transmethylation of a four-coordinate nickel(i) monocarbonyl species with methyl iodide

Abstract: The reaction of a nickel(i) carbonyl species with CH3I revealed the formation of (PNP)NiCOCH3 which differs from its zerovalent congener.

Cited by 57 publications

References 52 publications

Photochemically Driven Reverse Water‐Gas Shift at Ambient Conditions mediated by a Nickel Pincer Complex

Photochemically Driven Reverse Water‐Gas Shift at Ambient Conditions mediated by a Nickel Pincer Complex

A T‐Shaped Nickel(I) Metalloradical Species

Methyl Complexes of the Transition Metals

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