A Novel N,P,C Cage Complex Formed by Rearrangement of a Tricyclic Phosphirane Complex: On the Importance of Non-covalent Interactions

被引：14

作者：

Nesterov, Vitaly ^{[1
]}

Espinosa, Arturo ^{[2
]}

Schnakenburg, Gregor ^{[1
]}

Streubel, Rainer ^{[1
]}

机构：

[1] Univ Bonn, Inst Anorgan Chem, D-53121 Bonn, Germany

[2] Univ Murcia, Fac Quim, Dept Quim Organ, E-30100 Murcia, Spain

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2014年 / 20卷 / 23期

关键词：

cage compounds; noncovalent interactions; P ligands; rearrangement; tungsten; NITRILIUM PHOSPHANE-YLIDE; 3+2 CYCLOADDITION; CHEMISTRY; PSEUDOPOTENTIALS; DERIVATIVES; PROGRAM; MODEL; ATOMS;

D O I：

10.1002/chem.201305061

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reaction of Li/Cl P-CPh3 phosphinidenoid tungsten(0) complex 2 with dimethylcyanamide afforded tricyclic phosphirane complex 4, an unprecedented rearrangement of which led to the novel N,P,C cage complex 6. On the basis of DFT calculations, formation and intramolecular [3+2] cycloaddition of the transient nitrilium phosphane ylide complex 3 to a phenyl ring of the triphenylmethyl substituent to give 4 is proposed. Furthermore, theoretical evidence for terminal N-amidinophosphinidene complex 7, formed by [2+1] cycloelimination from 4, is provided, and the role of the electronic structure and non-covalent interactions of intermediate 7 discussed.

引用

页码：7010 / 7016

页数：7

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