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

共 31 条

[21] Room Temperature Reduction of CO2 to Methanol by Al-Based Frustrated Lewis Pairs and Ammonia Borane [J].

Menard, Gabriel ;

Stephan, Douglas W. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (06) :1796-+

[22] Reversible Metal-Free Carbon Dioxide Binding by Frustrated Lewis Pairs [J].

Moemming, Cornelia M. ;

Otten, Edwin ;

Kehr, Gerald ;

Froehlich, Roland ;

Grimme, Stefan ;

Stephan, Douglas W. ;

Erker, Gerhard .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (36) :6643-6646

[23]

Plack V, 1999, Z ANORG ALLG CHEM, V625, P1979, DOI 10.1002/(SICI)1521-3749(199912)625:12<1979::AID-ZAAC1979>3.0.CO

[24]

2-S

[25] Phosphination of Carbon Monoxide: A Simple Synthesis of Sodium Phosphaethynolate (NaOCP) [J].

Puschmann, Florian Frank ;

Stein, Daniel ;

Heift, Dominikus ;

Hendriksen, Coenradus ;

Gal, Zoltan A. ;

Gruetzmacher, Hans-Friedrich ;

Gruetzmacher, Hansjoerg .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (36) :8420-8423

[26] UNUSUALLY COORDINATED PHOSPHORUS-COMPOUNDS .41. PHOSPHAALKYNES - NEW BUILDING-BLOCKS IN SYNTHETIC CHEMISTRY [J].

REGITZ, M .

CHEMICAL REVIEWS, 1990, 90 (01) :191-213

[27] AB-INITIO STUDIES OF THE DIMERIZATON OF KETENE AND PHOSPHAKETENE [J].

SALZNER, U ;

BACHRACH, SM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (15) :6850-6855

[28] Molden: a pre- and post-processing program for molecular and electronic structures [J].

Schaftenaar, G ;

Noordik, JH .

JOURNAL OF COMPUTER-AIDED MOLECULAR DESIGN, 2000, 14 (02) :123-134

[29] A COMPARISON OF THE ENERGIES OF DOUBLE-BONDS OF 2ND-ROW ELEMENTS WITH CARBON AND SILICON [J].

SCHLEYER, PV ;

KOST, D .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (07) :2105-2109

[30] A comparison of density functional methods for the calculation of phosphorus-31 NMR chemical shifts [J].

van Wüllen, C .

PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2000, 2 (10) :2137-2144

← 1 2 3 4 →