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Arene C-H Amination at Nickel in Terphenyl–Diphosphine Complexes with Labile Metal–Arene Interactions

Herbert, David E. and Lara, Nadia C. and Agapie, Theodor (2013) Arene C-H Amination at Nickel in Terphenyl–Diphosphine Complexes with Labile Metal–Arene Interactions. Chemistry-A European Journal, 19 (48). pp. 16453-16460. ISSN 0947-6539. PMCID PMC3897266. doi:10.1002/chem.201302539.

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The meta-terphenyl diphosphine, m-P_2, 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-P_2)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=CH_3CN, CO, Ph_2CN_2), Ni^IX complexes (3-X: X=Cl, BF_4, N_3, N_3B(C_6F_5)_3), and [(m-P_2)Ni^(II)Cl_2] (4). Complex 2 reacts with substrates, such as diphenyldiazoalkane, sulfur ylides (Ph_2=CH_2), organoazides (RN_3: R=para-C_6H_4OMe, para-C_6H_4CF_3, 1-adamantyl), and N_2O with the locus of observed reactivity dependent on the nature of the substrate. These reactions led to isolation of an η^1-diphenyldiazoalkane adduct (2-Ph_2CN_2), 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.

Item Type:Article
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URLURL TypeDescription CentralArticle
Agapie, Theodor0000-0002-9692-7614
Additional Information:© 2013 Wiley-VCH Verlag GmbH & Co. Received: July 2, 2013. Article first published online: 14 Oct 2013. The authors thank Larry M. Henling for invaluable crystallographic assistance, the late Dr. Michael W. Day for solving the crystal structure of 4, and Caltech for generous funding and support. The Bruker KAPPA APEXII X-Ray diffractometer was purchased via an NSF CRIF:MU award to Caltech (CHE-0639094). The Gordon and Betty Moore Foundation, the Beckman Institute and the Sanofi-Aventis BRP are thanked for their support of the Molecular Observatory at Caltech and the SSRL beamline, operated for the DOE and supported by its Office of Biological and Environmental Research and by the NIH and NIGMS (P41 M103393) and the NCRR (P41RR001209).
Funding AgencyGrant Number
Gordon and Betty Moore FoundationUNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Caltech Molecular ObservatoryUNSPECIFIED
Department of Energy (DOE)UNSPECIFIED
NIHP41 M103393
Subject Keywords:amination; arenes; C H activation; group transfer; insertion reactions
Issue or Number:48
PubMed Central ID:PMC3897266
Record Number:CaltechAUTHORS:20140224-152357603
Persistent URL:
Official Citation:Herbert, D. E., Lara, N. C. and Agapie, T. (2013), Arene C[BOND]H Amination at Nickel in Terphenyl–Diphosphine Complexes with Labile Metal–Arene Interactions. Chem. Eur. J., 19: 16453–16460. doi: 10.1002/chem.201302539
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:43959
Deposited By: Ruth Sustaita
Deposited On:25 Feb 2014 00:02
Last Modified:10 Nov 2021 16:45

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