Reactivity of low-oxidation state tin compounds: an overview of the benefits of combining DFT Theory and experimental NMR spectroscopy

被引：2

作者：

De Proft, Frank ^{[1
]}

Broeckaert, Lies ^{[1
]}

Turek, Jan ^{[2
]}

Ruzicka, Ales ^{[2
]}

Willem, Rudolph ^{[3
]}

机构：

[1] Vrije Univ Brussel, Dept Gen Chem ALGC, B-1050 Brussels, Belgium

[2] Univ Pardubice, Fac Chem Technol, Dept Gen & Inorgan Chem, Pardubice 53210, Czech Republic

[3] Vrije Univ Brussel, Dept Mat & Chem MACH, B-1050 Brussels, Belgium

来源：

CANADIAN JOURNAL OF CHEMISTRY | 2014年 / 92卷 / 06期

关键词：

dicoordinate tin compounds; Sn-119 NMR spectroscopy; conceptual density functional theory; stannylenes and stannylones; reactivity; DENSITY-FUNCTIONAL THEORY; DIVALENT CARBON(0) COMPOUNDS; ORDER REGULAR APPROXIMATION; FRACTIONAL PARTICLE NUMBER; NUCLEAR-MAGNETIC-RESONANCE; FRONTIER-ELECTRON THEORY; DERIVATIVE DISCONTINUITIES; CHEMICAL-REACTIVITY; METAL ALKYLS; BASIS-SETS;

D O I：

10.1139/cjc-2013-0521

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reactivity and complexation properties of dicoordinated Sn(II) and Sn(0) compounds are reviewed. The (dominant) electrophilicity of the stannylenes was confirmed and quantified through density functional theory (DFT) based reactivity indices. For these compounds, combining theoretical DFT calculations and experimental nuclear magnetic resonance (NMR) spectroscopic results has evidenced their potential to undergo pi-complexation from aromatic pi clouds in addition to significantly stronger sigma-complexation. Moreover, their potential as Lewis bases was scrutinized in their interactions and reactions with iron and tungsten carbonyl Lewis acids. Finally, a prospective comparison of the reactivity of divalent stannylenes and stannylones, with a 0 oxidation state at the Sn atom, is presented.

引用

页码：447 / 461

页数：15

共 2 条

[1] Following the oxidation state of organosulfur compounds with NMR: Experimental data versus DFT calculations and database-powered NMR prediction
Szafranski, P. W.
Trybula, M. E.
Kasza, P.
Cegla, M. T.
JOURNAL OF MOLECULAR STRUCTURE, 2020, 1202
[2] Solid-state and high-resolution liquid 119Sn NMR spectroscopy of some monomeric, two-coordinate low-valent tin compounds:: Very large chemical shift anisotropies
Eichler, BE
Phillips, BL
Power, PP
Augustine, MP
INORGANIC CHEMISTRY, 2000, 39 (24) : 5450 - 5453

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