Heterobimetallic Dioxygen Activation: Synthesis and Reactivity of Mixed Cu−Pd and Cu−Pt Bis(μ-oxo) Complexes
- 1 June 2007
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 129 (25), 7990-7999
- https://doi.org/10.1021/ja071744g
Abstract
Heterobimetallic CuPd and CuPt bis(μ-oxo) complexes have been prepared by the reaction of (PPh3)2MO2 (M = Pd, Pt) with LCu(I) precursors (L = β-diketiminate and di- and triamine ligands) and characterized by low-temperature UV−vis, resonance Raman, and 1H and 31P{1H} NMR spectroscopy in conjunction with DFT calculations. The complexes decompose upon warming to yield OPPh3, and in one case this was shown to occur by an intramolecular process through crossover experiments using double-labeling (oxo and phosphine). The reactivity of one of the complexes, LMe2Cu(μ-O)2Pt(PPh3)2 (LMe2 = β-diketiminate), with a variety of reagents including CO2, 2,4-di-tert-butylphenol, 2,4-di-tert-butylphenolate, [NH4][PF6], and dihydroanthracene, was compared to that of homometallic Pt2 and Cu2 counterparts. Unlike typical [Cu2(μ-O)2]2+ cores which have electrophilic oxo groups, the oxo groups in the [Cu(μ-O)2Pt]+ core behave as bases and nucleophiles, similar to previously described Pt2 compounds. In addition, however, the [Cu(μ-O)2Pt]+ core is capable of oxidatively coupling 2,4-di-tert-butylphenol and 2,4-di-tert-butylphenolate. Theoretical evaluation of the electron affinities, basicities, and H-atom transfer kinetics and thermodynamics of the Cu2 and CuM (M = Pd, Pt) cores showed that the latter are more basic and form stronger O−H bonds.Keywords
This publication has 70 references indexed in Scilit:
- Critical Assessment of the Performance of Density Functional Methods for Several Atomic and Molecular PropertiesJournal of Chemical Theory and Computation, 2007
- Heterobimetallic Activation of Dioxygen: Characterization and Reactivity of Novel Cu(I)−Ge(II) ComplexesInorganic Chemistry, 2006
- Fine‐Tuning the Electronic Properties of Highly Stable Organometallic CuIII Complexes Containing Monoanionic Macrocyclic LigandsChemistry – A European Journal, 2005
- Oxidant types in copper–dioxygen chemistry: the ligand coordination defines the Cu n -O2 structure and subsequent reactivityJBIC Journal of Biological Inorganic Chemistry, 2004
- Formation, Characterization, and Reactivity of Bis(μ-oxo)dinickel(III) Complexes Supported by A Series of Bis[2-(2-pyridyl)ethyl]amine LigandsJournal of the American Chemical Society, 2001
- Dioxygen activation by a neutral β-diketiminato copper(i) ethylene complexChemical Communications, 2001
- Spectroscopic and Electronic Structural Studies of the Cu(III)2Bis-μ-oxo Core and Its Relation to the Side-On Peroxo-Bridged DimerJournal of the American Chemical Society, 1999
- C−H Bond Activation by a Ferric Methoxide Complex: A Model for the Rate-Determining Step in the Mechanism of LipoxygenaseJournal of the American Chemical Society, 1997
- New aspects of oxypalladation of alkenesAccounts of Chemical Research, 1990
- Metal-ligand bond-energies in organometallic compoundsPublished by Walter de Gruyter GmbH ,1985