Coulomb repulsion versus cycloaddition: formation of anionic four-membered rings from sodium phosphaethynolate, Na(OCP)

被引：118

作者：

Heift, Dominikus ^{[1
]}

Benko, Zoltan ^{[1
]}

Gruetzmacher, Hansjoerg ^{[1
,2
]}

机构：

[1] ETH, Dept Chem & Appl Biosci, CH-8093 Zurich, Switzerland

[2] Sun Yat Sen Univ, LIFM, Guangzhou 510275, Guangdong, Peoples R China

来源：

DALTON TRANSACTIONS | 2014年 / 43卷 / 02期

基金：

瑞士国家科学基金会;

关键词：

CARBON-DIOXIDE; AB-INITIO; ALKYLIDYNEPHOSPHANES; ALKYLIDYNEARSANES; PHOSPHINES; INSERTION; LIGANDS; KETENE; BONDS; CO2;

D O I：

10.1039/c3dt52359d

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Carbon dioxide and two equivalents of Na(OCP) form, in an equilibrium reaction, a CO2 adduct of the composition Na-2(P2C3O4). The anion of this salt, [O2C-P(CO)(2)P](2-), is built up by a four-membered 1,3-diphosphetane-2,4-dione ring and a carboxylate unit attached to one of the phosphorus atoms. A remarkable pi-delocalization was observed within the OCPCO moiety. The stepwise reaction mechanism leading to Na-2(P2C3O4) was investigated with quantum chemical calculations. Accompanied by the release of CO2, Na-2(P2C3O4) reacts with both 2-iodopropane and 4,4',4 ''-trimethoxytriphenylmethyl chloride to form four-membered cyclic anions. For comparison the analogous reactions were performed with Na(OCP) instead of Na-2(P2C3O4) and the results are discussed in detail.

引用

页码：831 / 840

页数：10

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