Correlations and Contrasts in Homo- and Heteroleptic Cyclic (Alkyl)(amino)carbene-Containing Pt0 Complexes

被引：14

作者：

Arnold, Nicole ^{[1
]}

Braunschweig, Holger ^{[1
]}

Brenner, Peter B. ^{[1
]}

Celik, Mehmet Ali ^{[1
]}

Dewhurst, Rian D. ^{[1
]}

Haehnel, Martin ^{[1
]}

Kramer, Thomas ^{[1
]}

Krummenacher, Ivo ^{[1
]}

Marder, Todd B. ^{[1
]}

机构：

[1] Univ Wurzburg, Inst Anorgan Chem, D-97074 Wurzburg, Germany

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2015年 / 21卷 / 35期

关键词：

carbenes; Lewis bases; oxidative addition; phosphine ligands; platinum; TRANSITION-METAL-COMPLEXES; ALKYL AMINO CARBENES; OXIDATIVE ADDITION; PLATINUM COMPLEXES; STABLE CARBENES; BORYL LIGANDS; LEWIS-BASES; REACTIVITY; CHEMISTRY; COMPOUND;

D O I：

10.1002/chem.201502048

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

An improved synthetic route to homoleptic complex [Pt(CAAC(Me))(2)] (CAAC=cyclic (alkyl)(amino)carbenes) and convenient routes to new heteroleptic complexes of the form [Pt(CAAC(Me))(PR3)] are presented. Although the homoleptic complex was found to be inert to many reagents, oxidative addition and metal-only Lewis pair (MOLP) formation was observed from one of the heteroleptic complexes. The spectroscopic, structural, and electrochemical properties of the zero-valent complexes were explored in concert with density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations. The homoleptic [Pt(CAAC)(2)] and heteroleptic [Pt(CAAC)(PR3)] complexes were found to be similar in their spectroscopic and structural properties, but their electrochemical behavior and reactivity differ greatly. The unusually strong color of the CAAC-containing Pt-0 complexes was investigated by TD-DFT calculations and attributed to excitations into the LUMOs of the complexes, which are predominantly composed of bonding pi interactions between Pt and the CAAC carbon atoms.

引用

页码：12357 / 12362

页数：6

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