482322-72-5Relevant academic research and scientific papers
Heterobimetallic dioxygen activation: Synthesis and reactivity of mixed Cu-Pd and Cu-Pt bis(μ-oxo) complexes
York, John T.,Llobet, Antoni,Cramer, Christopher J.,Tolman, William B.
, p. 7990 - 7999 (2007)
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(PPh 3)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-terf-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.
Intermediates in reactions of copper(I) Complexes with N-Oxides: from the formation of stable adducts to Oxo Transfer
Hong, Sungjun,Gupta, Aaio K.,Tolman, William B.
, p. 6323 - 6325 (2009/10/23)
Reactions of copper(I) complexes of bidentate N-donor supporting ligands with pyridine- and trimethylamine-N-oxides or PhIO were explored. Key results include the identification of novel copper(I) Noxide adducts, aryl substituent hydroxylation, and bis(μ-
Heterobimetallic activation of dioxygen: Characterization and reactivity of novel Cu(I)-Ge(II) complexes
York, John T.,Young Jr., Victor G.,Tolman, William B.
, p. 4191 - 4198 (2008/10/09)
Reaction of the known germylene Ge[N(SiMe3)2] 2 and a new heterocyclic variant Ge[(NMes)2(CH) 2] with [LMe2Cu]2 (LMe2 = the β-diketiminate derived from 2-(2,6-dimethylphenyl)amino-4-(2,6- dimethylphenyl)imino-2-pentene) yielded novel Cu(I)-Ge(II) complexes L Me2Cu-Ge[(NMes)2(CH)2] (1a) and L Me2Cu-Ge[N(SiMe3)2]2 (1b), which were characterized by spectroscopy and X-ray crystallography. The lability of the Cu(I)-Ge(II) bond in 1a and b was probed by studies of their reactivity with benzil, PPh3, and a N-heterocyclic carbene (NHC). Notably, both complexes are cleaved rapidly by PPh3 and the NHC to yield stable Cu(I) adducts (characterized by X-ray diffraction) and the free germylene. In addition, the complexes are highly reactive with O2 and exhibit chemistry which depends on the bound germylene. Thus, oxygenation of 1a results in scission and formation of thermally unstable LMe2CuO2, which subsequently decays to [(LMe2Cu)2(μ-O) 2], while 1b yields LMe2Cu(μ-O) 2Ge[N(SiMe3)2]2, a novel heterobimetallic intermediate having a [CuIII(μ-O) 2GeIV]3+ core. The isolation of the latter species by direct oxygenation of a Cu-(I)-Ge(II) precursor represents a new route to heterobimetallic oxidants comprising copper.
