Isolation of a Cationic Platinum(II) σ-Silane Complex

被引：28

作者：

Rios, Pablo

Fouilloux, Hugo

Vidossich, Pietro ^{[3
,4
]}

Diez, Josefina ^{[5
]}

Lledos, Agusti ^{[3
]}

Conejero, Salvador ^{[1
,2
]}

机构：

[1] CSIC, Ctr Innovac Quim Avanzada ORFEO CINCA, Dept Quim Inorgan, IIQ, Avda Americo Vespucio 49, Seville 41092, Spain

[2] Univ Seville, Avda Americo Vespucio 49, Seville 41092, Spain

[3] Univ Autonoma Barcelona, Dept Quim, Ctr Innovac Quim Avanzada ORFEO CINCA, Campus UAB, Cerdanyola Del Valles 08193, Spain

[4] Univ Andes, Dept Chem, COBO Computat Bioorgan Chem Bogota, Bogota, Colombia

[5] Univ Oviedo, Dept Quim Organ & Inorgan, Unidad Asociada CSIC, Lab Compuestos Organomet & Catalisis, E-33006 Oviedo, Spain

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2018年 / 57卷 / 12期

关键词：

density-functional calculations; platinum; silane; structure elucidation; x-ray diffraction; SI-H; SPECTROSCOPIC CHARACTERIZATION; BOND ACTIVATION; C-H; ETA(2)-SILANE; COORDINATION; RUTHENIUM; DYNAMICS; H-2;

D O I：

10.1002/anie.201712791

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The platinum complex [Pt((IBuPr)-Bu-t-Pr-i')((IBuPr)-Bu-t-Pr-i)][BArF] interacts with tertiary silanes to form stable (<0 degrees C) mononuclear Pt-II sigma-SiH complexes [Pt((IBuPr)-Bu-t-Pr-i')((IBuPr)-Bu-t-Pr-i)(eta(1)-HSiR3)][BArF]. These compounds have been fully characterized, including X-ray diffraction methods, as the first examples for platinum. DFT calculations (including electronic topological analysis) support the interpretation of the coordination as an unusual eta(1)-SiH. However, the energies required for achieving a eta(2)-SiH mode are rather low, and is consistent with the propensity of these derivatives to undergo Si-H cleavage leading to the more stable silyl species [Pt(SiR3)((IBuPr)-Bu-t-Pr-i)(2)]-[BArF] at room temperature.

引用

页码：3217 / 3221

页数：5

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