Nickel Complexes with Carbonyl, Isocyanide, and Carbene Ligands

Kubiak, Clifford P.; Simón-Manso, Eugenio

doi:10.1016/b0-08-045047-4/00099-6

Cited by 1 publication

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“…In contrast to the well-known ability of Ni(0) to coordinate and activate small gaseous molecules, a comparable appreciation of the reactivity of Ni(I) is very much still in its infancy, predominantly because there are relatively few isolated and fully characterized Ni(I) complexes . Small molecule coordination/activation at monovalent nickel is therefore first and foremost of considerable fundamental interest, , but also of practical importance because Ni(I) is known to be central to a number of enzymatic processes .…”

Section: Introductionmentioning

confidence: 99%

Stereoelectronic Effects in C–H Bond Oxidation Reactions of Ni(I) N-Heterocyclic Carbene Complexes

et al. 2014

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Activation of O 2 by the three-coordinate Ni(I) ring-expanded N-heterocyclic carbene complexes Ni(NHC)(PPh 3 )Br (NHC = 6-Mes, 7-Mes) produced the dimeric Ni(II) complexes Ni(6-Mes)(Br)(µ-OH)(µ-O-6-Mes′)NiBr (3) and Ni(7-Mes)(Br)(µ-OH)(µ-O-7-Mes′)NiBr (4) containing oxidized ortho-mesityl groups from one of the carbene ligands. Mass spectrometry was consistent with bis-µ-aryloxy compounds also being formed in these reactions. Low temperature UV-visible spectroscopy showed that the reaction between Ni(6-Mes)(PPh 3 )Br and O 2 was too fast even at ca. -80 °C to yield any observable intermediates. Addition of O 2 to Ni(I) precursors containing a less donating diamidocarbene (6-MesDAC) or the less bulky 6-/7-membered ring diaminocarbene ligands (6-/7-o-Tol) proceeded quite differently, affording phosphine and carbene oxidation products (Ni(O=PPh 3 ) 2 Br 2 and (6-MesDAC)=O) and mononuclear dibromido Ni(II) complexes (Ni(6-/7-o-Tol)(PPh 3 )Br 2 ) respectively.3

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