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Arene C-H amination at nickel in terphenyl-diphosphine complexes with labile metal-arene interactions.

ABSTRACT: The meta-terphenyl diphosphine, m-P2, 1, was utilized to support Ni centers in the oxidation states 0, I, and II. A series of complexes bearing different substituents or ligands at Ni was prepared to investigate the dependence of metal-arene interactions on oxidation state and substitution at the metal center. Complex (m-P2)Ni (2) shows strong Ni(0)-arene interactions involving the central arene ring of the terphenyl ligand both in solution and the solid state. These interactions are significantly less pronounced in Ni(0) complexes bearing L-type ligands (2-L: L=CH3CN, CO, Ph2CN2), Ni(I)X complexes (3-X: X=Cl, BF4, N3, N3B(C6F5)3), and [(m-P2)Ni(II)Cl2] (4). Complex 2 reacts with substrates, such as diphenyldiazoalkane, sulfur ylides (Ph2 S=CH2 ), organoazides (RN3: R=para-C6H4OMe, para-C6H4CF3, 1-adamantyl), and N2O with the locus of observed reactivity dependent on the nature of the substrate. These reactions led to isolation of an ?(1)-diphenyldiazoalkane adduct (2-Ph2CN2), methylidene insertion into a Ni-P bond followed by rearrangement of a nickel-bound phosphorus ylide (5) to a benzylphosphine (6), Staudinger oxidation of the phosphine arms, and metal-mediated nitrene insertion into an arene C-H bond of 1, all derived from the same compound (2). Hydrogen-atom abstraction from a Ni(I)-amide (9) and the resulting nitrene transfer supports the viability of Ni-imide intermediates in the reaction of 1 with 1-azido-arenes.

SUBMITTER: Herbert DE

PROVIDER: S-EPMC3897266 | biostudies-literature | 2013 Nov

REPOSITORIES: biostudies-literature

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Arene C-H amination at nickel in terphenyl-diphosphine complexes with labile metal-arene interactions.

Herbert David E DE Lara Nadia C NC Agapie Theodor T

Chemistry (Weinheim an der Bergstrasse, Germany) 20131014 48

The meta-terphenyl diphosphine, m-P2, 1, was utilized to support Ni centers in the oxidation states 0, I, and II. A series of complexes bearing different substituents or ligands at Ni was prepared to investigate the dependence of metal-arene interactions on oxidation state and substitution at the metal center. Complex (m-P2)Ni (2) shows strong Ni(0)-arene interactions involving the central arene ring of the terphenyl ligand both in solution and the solid state. These interactions are significant ...[more]

PMID: 24127196

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Project description:Metalation of the deprotonated dipyrrin (AdFL)Li with NiCl2(py)2 afforded the divalent Ni product (AdFL)NiCl(py)2 (1) (AdFL: 1,9-di(1-adamantyl)-5-perfluorophenyldipyrrin; py: pyridine). To generate a reactive synthon on which to explore oxidative group transfer, we used potassium graphite to reduce 1, affording the monovalent Ni synthon (AdFL)Ni(py) (2) and concomitant production of a stoichiometric equivalent of KCl and pyridine. Slow addition of mesityl- or 1-adamantylazide in benzene to 2 afforded the oxidized Ni complexes (AdFL)Ni(NMes) (3) and (AdFL)Ni(NAd) (4), respectively. Both 3 and 4 were characterized by multinuclear NMR, EPR, magnetometry, single-crystal X-ray crystallography, theoretical calculations, and X-ray absorption spectroscopies to provide a detailed electronic structure picture of the nitrenoid adducts. X-ray absorption near edge spectroscopy (XANES) on the Ni reveals higher energy Ni 1s → 3d transitions (3: 8333.2 eV; 4: 8333.4 eV) than NiI or unambiguous NiII analogues. N K-edge X-ray absorption spectroscopy performed on 3 and 4 reveals a common low-energy absorption present only for 3 and 4 (395.4 eV) that was assigned via TDDFT as an N 1s promotion into a predominantly N-localized, singly occupied orbital, akin to metal-supported iminyl complexes reported for iron. On the continuum of imido (i.e., NR2-) to iminyl (i.e., 2NR-) formulations, the complexes are best described as NiII-bound iminyl species given the N K-edge and TDDFT results. Given the open-shell configuration (S = 1/2) of the iminyl adducts, we then examined their propensity to undergo nitrenoid-group transfer to organic substrates. The adamantyl complex 4 readily consumes 1,4-cyclohexadiene (CHD) via H-atom abstraction to afford the amide (AdFL)Ni(NHAd) (5), whereas no reaction was observed upon treatment of the mesityl variant 3 with excess amount of CHD over 3 hours. Toluene can be functionalized by 4 at room temperature, exclusively affording the N-1-adamantyl-benzylidene (6). Slow addition of the organoazide substrate (4-azidobutyl)benzene (7) with 2 exclusively forms 4-phenylbutanenitrile (8) as opposed to an intramolecular cyclized pyrrolidine, resulting from facile β-H elimination outcompeting H-atom abstraction from the benzylic position, followed by rapid H2-elimination from the intermediate Ni hydride ketimide intermediate.

Dataset Information

Arene C-H amination at nickel in terphenyl-diphosphine complexes with labile metal-arene interactions.

Publications

Arene C-H amination at nickel in terphenyl-diphosphine complexes with labile metal-arene interactions.

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