Pressure-Enhanced C-H Bond Activation in Chloromethane Platinum(II) Complexes

被引：6

作者：

Schmitz, Dominik ^{[1
]}

Kalter, Marcel ^{[1
]}

Dunbar, Andrew C. ^{[1
]}

Voest, Marcel ^{[1
]}

Fischer, Andreas ^{[1
]}

Batke, Kilian ^{[1
]}

Eickerling, Georg ^{[1
]}

Ruhland, Klaus ^{[1
]}

Ebad-Allah, Jihaan ^{[1
,2
]}

Kuntscher, Christine ^{[1
]}

Scherer, Wolfgang ^{[1
]}

机构：

[1] Univ Augsburg, Inst Phys, Univ Str 1, D-86135 Augsburg, Germany

[2] Tanta Univ, Dept Phys, Tanta 31527, Egypt

来源：

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY | 2020年 / 2020卷 / 01期

关键词：

Bond activation; sigma-Complexes; Platinum; Charge density; Density functional calculations; DENSITY-FUNCTIONAL THEORY; SIGMA-ALKANE COMPLEX; ANAGOSTIC INTERACTIONS; ELECTRON LOCALIZATION; METHANE COMPLEX; AB-INITIO; METAL; COORDINATION; STRENGTHS; SPECTRA;

D O I：

10.1002/ejic.201901117

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The nature of the interaction between chloromethanes CH4-nCln and Pt(II) complexes has been studied by high-pressure X-ray diffraction and infrared spectroscopy in combination with DFT calculations. In case of electron rich complexes such as d(8)-Pt(btz-N,N ')(phenyl)L with L = phenyl, Cl, Br and btz = 2,2 '-Bi-5,6-dihydro-4H-1,3-thiazine stable chloroform adducts with bridging hydrogen atoms in the eta(1)(C-H)Pt moieties were isolated which display highly activated C-H bonds. This activation is a consequence of a pronounced Pt(d(z2))->sigma*(C-H) back donation and is signaled by large red-shifts of the isolated nu(is)(C-H) stretching modes. The extent of the C-H bond activation and covalent Pt-H bond formation in the eta(1)(C-H)Pt moieties is thereby controlled by (i) the sigma/pi donor capabilities of the ligands L, (ii) the orientation of the coordinating C-H bond with regard to the Pt(d(z2)) orbital and (iii) the applied pressure.

引用

页码：79 / 83

页数：5

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