Primary aliphatic amine complexes of transition-metal halides

Kenessey, G.; Carson, B.R.; Allan, J.R.; Wadsten, T.; Liptay, G.

doi:10.1007/bf01979559

Cited by 4 publications

(4 citation statements)

References 8 publications

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“…However, the components of the quenching mixture must be elucidated in order to determine the identity and molar absorptivity of the EnT acceptor(s) to utilize Förster theory quantitatively in examining this hypothesis. Turning to classic reports − describing monodentate primary and secondary amine ligands binding to Ni(II), the available information is insufficient due to the lack of both crystallographic characterization and speciation studies in DMAc solution.…”

Section: Resultssupporting

confidence: 88%

Energy Transfer to Ni-Amine Complexes in Dual Catalytic, Light-Driven C–N Cross-Coupling Reactions

2019

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Dual catalytic light-driven cross-coupling methodologies utilizing a Ni(II) salt with a photocatalyst (PC) have emerged as promising methodologies to forge aryl C−N bonds under mild conditions. The recent discovery that the PC can be omitted and the Ni(II) complex directly photoexcited suggests that the PC may perform energy transfer (EnT) to the Ni(II) complex, a mechanistic possibility that has recently been proposed in other systems across dual Ni photocatalysis. Here, we report the first studies in this field capable of distinguishing EnT from electron transfer (ET), and the results are consistent with Forster-type EnT from the excited state [Ru(bpy) 3 ]Cl 2 PC to Ni-amine complexes. The structure and speciation of Ni-amine complexes that are the proposed EnT acceptors were elucidated by crystallography and spectroscopic binding studies. With the acceptors known, quantitative Forster theory was utilized to predict the ratio of quenching rate constants upon changing the PC, enabling selection of an organic phenoxazine PC that proved to be more effective in catalyzing C−N cross-coupling reactions with a diverse selection of amines and aryl halides.

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Section: Resultssupporting

confidence: 88%

Energy Transfer to Ni-Amine Complexes in Dual Catalytic, Light-Driven C–N Cross-Coupling Reactions

2019

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“…The coordination of amines to low valent transition metal centers represents a cornerstone of inorganic chemistry, and, relevantly, a large variety of amine containing metal complexes have been reported to exhibit useful properties . Activation of the amine ligand has been observed within a number of low valent metal halides, usually occurring via well-defined reaction pathways …”

Section: Introductionmentioning

confidence: 99%

Oxidative Dimerization of Triarylamines Promoted by WCl₆, Including the Solid State Isolation and the Crystallographic Characterization of a Triphenylammonium Salt

et al. 2015

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The triphenylammonium salt [NHPh3][WCl6], 1, and the product of the C-C dimerization of triphenylamine, Ph2N(C6H4)2NPh2, 2, were afforded from the reaction between WCl6 and NPh3 in CH2Cl2. Compound 2 was isolated in 43% yield upon hydrolysis of the reaction mixture. The X-ray structure of 1 provides the first crystallographic characterization of the triphenylammonium ion. Combined EPR and DFT studies gave insight into the reaction mechanism, and allowed the identification of WCl5···[Cl(C6H4)NPh2] as a presumable key intermediate. The reactions of WCl6 with 4-bromotriphenylamine, 4,4'-dimethyltriphenylamine, 9-phenylcarbazole, followed by hydrolytic treatment, led to the dimerization products 3-6, in admixture with variable amounts of the parent amines. N,N,N',N'-tetrakis(4-bromophenyl)-[1,1'-biphenyl]-4,4'-diamine, 3, was isolated in 60% yield from the reaction of WCl6 with 4,4'-dibromotriphenylamine.

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“…Meanwhile, external stimuli such as solvents [9a] and ions [12] are known to induce conformation switching. Since crystal structure of [Ni(NH 2 CH 3 ) 6 ] 2+ has not been reported, [13] there is lack of experimental evidence that confirms its conformation in the solid‐state. In addition, recent study found methylamine complexes may undergo structural transformation due to the release of methylamine [14] .…”

Section: Introductionmentioning

confidence: 99%

Anion‐Directed Conformation Switching and Trigonal Distortion in Hexakis(methylamine)nickel(II) Cations

et al. 2022

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The homoleptic [Ni(NH2CH3)6]2+ cations have dozens of energetically feasible conformational isomers (conformers), and we herein show their conformation is tunable using counter anions. The reaction of Ni(NO3)2 or NiCl2 with aqueous methylamine in dimethylformamide gave [Ni(NH2CH3)6](NO3)2 (1) or [Ni(NH2CH3)6]Cl2 (2) in which methylamine ligands have axial or equatorial orientation with respect to the three‐fold principal axis, respectively. Interestingly, the conformation of methylamine ligands affects geometry around nickel(II) so that the nickel octahedron is trigonally compressed in 1, whereas it is trigonally elongated in 2, causing different visible light absorption properties between 1 and 2. Density functional theory calculations showed that nitrate anions stabilize the axial conformer through two‐point hydrogen bonding interactions with methylamines, whereas spherical chloride anions promote deformation of the axial conformer into the equatorial conformer through formation of three‐point hydrogen bonding interactions.

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Primary aliphatic amine complexes of transition-metal halides

Cited by 4 publications

References 8 publications

Energy Transfer to Ni-Amine Complexes in Dual Catalytic, Light-Driven C–N Cross-Coupling Reactions

Energy Transfer to Ni-Amine Complexes in Dual Catalytic, Light-Driven C–N Cross-Coupling Reactions

Oxidative Dimerization of Triarylamines Promoted by WCl₆, Including the Solid State Isolation and the Crystallographic Characterization of a Triphenylammonium Salt

Anion‐Directed Conformation Switching and Trigonal Distortion in Hexakis(methylamine)nickel(II) Cations

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Primary aliphatic amine complexes of transition-metal halides

Cited by 4 publications

References 8 publications

Energy Transfer to Ni-Amine Complexes in Dual Catalytic, Light-Driven C–N Cross-Coupling Reactions

Energy Transfer to Ni-Amine Complexes in Dual Catalytic, Light-Driven C–N Cross-Coupling Reactions

Oxidative Dimerization of Triarylamines Promoted by WCl6, Including the Solid State Isolation and the Crystallographic Characterization of a Triphenylammonium Salt

Anion‐Directed Conformation Switching and Trigonal Distortion in Hexakis(methylamine)nickel(II) Cations

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Oxidative Dimerization of Triarylamines Promoted by WCl₆, Including the Solid State Isolation and the Crystallographic Characterization of a Triphenylammonium Salt