Formation of Hybrid Guanidine-Stabilized Bis(μ-oxo)-dicopper Cores in Solution: Electronic and Steric Perturbations

被引：27

作者：

Herres-Pawlis, Sonja ^{[1
]}

Haase, Roxana ^{[2
]}

Verma, Pratik ^{[3
]}

Hoffmann, Alexander ^{[1
]}

Kang, Peng ^{[3
]}

Stack, T. Daniel P. ^{[3
]}

机构：

[1] Rhein Westfal TH Aachen, Lehrstuhl Bioanorgan Chem, D-52074 Aachen, Germany

[2] Univ Paderborn, Dept Chem, Anorgan Chem, D-33098 Paderborn, Germany

[3] Stanford Univ, Dept Chem, Stanford, CA 94305 USA

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2015年 / 32期

基金：

美国国家卫生研究院;

关键词：

Bioinorganic chemistry; Enzyme models; Copper; Bridging ligands; Density functional calculations; SIDE-ON PEROXO; SECONDARY DIAMINE LIGAND; TYROSINASE MODEL SYSTEM; COPPER-DIOXYGEN; PEROXODICOPPER(II) COMPLEX; REACTIVITY; HYDROXYLATION; MECHANISM; OXO; TRIS(PYRAZOLYL)METHANE;

D O I：

10.1002/ejic.201500884

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A series of new hybrid peralkylated amine-guanidine ligands based on a 1,3-propanediamine backbone and their Cu-O-2 chemistry is reported. The copper(I) complexes react readily with O-2 at low temperatures in aprotic solvents with weakly coordinating anions to form exclusively bis(mu-oxo) dicopper species (O). Variation of the substituents on each side of the hybrid bidentate ligand reveal that less sterically demanding amine and guanidine substituents increase not only the thermal stability of the formed O cores but also enhance innersphere phenolate hydroxylation pathways. TD-DFT analysis on selected guanidine-amine O species suggest that the additional visible-wavelength feature observed is a guanidine pi* -> Cu2O2 LMCT, which appears along with the classic oxo-sigma(u)* -> Cu-III and pi(sigma)* -> Cu-III LMCT transitions.

引用

页码：5426 / 5436

页数：11

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