Facile Ligand Oxidation and Ring Nitration in Ruthenium Complexes Derived from a Ligand with Dicarboxamide-N and Phosphine-P Donors
作者:Nicole L. Fry、Michael J. Rose、Crystal Nyitray、Pradip K. Mascharak
DOI:10.1021/ic801243a
日期:2008.12.15
The reaction of the tetradentate dicarboxamide ligand 1,2-bis-N[2'(diphenylphosphanyl)benzoyl]diaminobenzene (dppbH(2)) with RuCl3 in DMF or ethanol results in metal-mediated ligand oxidation and formation of the diamagnetic Ru(II) complex [(dppQ)Ru(Cl)(2)] (1) with N2P2 chromophore. The o-phenylenedicarboxamide portion of the dppb(2-) ligand is oxidized to a o-benzoquinonediimine (bqdi) moiety in [(dppQ)Ru(Cl)(2)]. Presence of oxygen accelerates the ligand oxidation process. Unlike other tetradentate dicarboxamide ligands with pyridine-N, phenolato-O, or thiolato-S donors, dppb(2-) provides stability to the +2 oxidation state of ruthenium and facilitates oxidation of the coordinated ligand frame. Results of spectroscopic and redox studies strongly support the +2 oxidation state of Ru in 1. Exposure of 1 to NO(g) does not lead to formation of any metal nitrosyl; instead, the bqdi ring is nitrated to afford [(NO(2)dppQ)Ru(Cl)(2)] (2).
Metal-amidato complexes: Synthesis, characterization, and reactivity of a diamidato-bis(phosphine) nickel(II) complex
作者:Daniel N. Huh、Joseph B. Gibbons、Ryan S. Haywood、Curtis E. Moore、Arnold L. Rheingold、Michael J. Ferguson、Christopher J.A. Daley
DOI:10.1016/j.ica.2014.08.033
日期:2014.11
Reaction of 1,2-bis-N-[2-(diphenyl-phosphanyl)benzoyl]diaminobenzene (H2N2P2: H(2)1) with Ni(ClO4)(2) produced the corresponding tetradentate diamidato-bis(phosphine) nickel(II) complex Ni(N2P2) (2). Reactivity studies of 2 with reductants yielded the orthometallated product [M+][Ni(N2PC)] ([M+][3]), where M = Cp-2*Co-III or NBu4 and N2PC = N-((2-diphenylphosphino)-benzoyl)-N'-((1-phen-2-idyl)oxomethyl)-1,2-diaminobenzene, via reductive cleavage of one of the PPh2 groups of H(2)1. The synthesis and characterization of the complexes are described. (C) 2014 Elsevier B.V. All rights reserved.