Activation of CO2 and CS2 by (Me3Si)(i-Pr2P)NH and its zinc complex

被引：15
作者：
Dickie, Diane A. [1 ]
Ulibarri-Sanchez, Raymond P., III [1 ,2 ]
Jarman, Paul J. [1 ]
Kemp, Richard A. [1 ,2 ]
机构：
[1] Univ New Mexico, Dept Chem & Chem Biol, Albuquerque, NM 87131 USA
[2] Sandia Natl Labs, Adv Mat Lab, Albuquerque, NM 87106 USA
来源：
POLYHEDRON | 2013年 / 58卷
基金：
美国国家科学基金会;
关键词：
Main group compounds; X-ray crystallography; NMR; Synthesis; CS2; CO2; FRUSTRATED LEWIS PAIRS; CARBON-DIOXIDE BINDING; MOLECULAR-STRUCTURE; C-H; REACTIVITY; CRYSTAL; ALUMINUM;
D O I：
10.1016/j.poly.2012.10.048
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The reaction of (Me3Si)(i-Pr2P)NH with ZnEt2 gives the complex {[(Me3Si)(i-Pr2P)N]ZnEt}(2), which was characterized by multinuclear NMR spectroscopy and X-ray crystallography. This Zn complex reacts with CO2 to give an adduct with the proposed formula of [(Me3Si)N(i-Pr2PCO2)]ZnEt that undergoes further transformation into the crystallographically characterized di-adduct [(Me3Si)N(i-Pr2PCO2)](2)Zn, in addition to a Zn-6 cluster containing both P-CO2 adducts and fragments of the isocyanate i-Pr2P-N=C=O. These reaction pathways have been separately observed in related group 2 and group 14 complexes, but not previously within the same molecule. Reactions with the related heteroallene CS2 were also examined. The free ligand (Me3Si)(i-Pr2P)NH reacts with CS2 to form a bright red, crystalline adduct (Me-3 Si)[P(i-Pr)(2)(CS2)]NH. This adduct was treated with ZnEt2 to provide the same product that is obtained from the reaction of {[(Me3Si)(i-Pr2P)N]ZnEt}(2) with CS2, proposed to be a dithiocarbamate complex, with the CS2 bound to the N instead of the P atom. (C) 2012 Elsevier Ltd. All rights reserved.
引用
收藏
页码：92 / 98
页数：7
相关论文
共 52 条
[1]  
[Anonymous], 1882, NEW REMEDIES, V9, P151
[2]   Geminal Phosphorus/Aluminum-Based Frustrated Lewis Pairs: C-H versus C≡C Activation and CO2 Fixation [J].
Appelt, Christian ;
Westenberg, Hauke ;
Bertini, Federica ;
Ehlers, Andreas W. ;
Slootweg, J. Chris ;
Lammertsma, Koop ;
Uhl, Werner .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (17) :3925-3928
[3]   Tandem Frustrated Lewis Pair/Tris(pentafluorophenyl)borane-Catalyzed Deoxygenative Hydrosilylation of Carbon Dioxide [J].
Berkefeld, Andreas ;
Piers, Warren E. ;
Parvez, Masood .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (31) :10660-10661
[4]   Preorganized Frustrated Lewis Pairs [J].
Bertini, Federica ;
Lyaskoyskyy, Volodymyr ;
Timmer, Brian J. J. ;
de Kanter, Frans J. J. ;
Lutz, Martin ;
Ehlers, Andreas W. ;
Slootweg, J. Chris ;
Lammertsma, Koop .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2012, 134 (01) :201-204
[5]   Frustrated Lewis Pairs and Ring-Opening of THF, Dioxane, and Thioxane [J].
Birkmann, Birgit ;
Voss, Tanja ;
Geier, Stephen J. ;
Ullrich, Matthias ;
Kehr, Gerald ;
Erker, Gerhard ;
Stephan, Douglas W. .
ORGANOMETALLICS, 2010, 29 (21) :5310-5319
[6]   Reactivity of Lewis pairs (R2PCH2AlMe2)2 with carbon dioxide [J].
Boudreau, Josee ;
Courtemanche, Marc-Andre ;
Fontaine, Frederic-Georges .
CHEMICAL COMMUNICATIONS, 2011, 47 (39) :11131-11133
[7]   Cationic Group 4 Metallocene-(o-Phosphanylaryl)oxido Complexes: Synthetic Routes to Transition-Metal Frustrated Lewis Pairs [J].
Chapman, Andy M. ;
Haddow, Mairi F. ;
Wass, Duncan F. .
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2012, (09) :1546-1554
[8]   Frustrated Lewis Pairs beyond the Main Group: Synthesis, Reactivity, and Small Molecule Activation with Cationic Zirconocene-Phosphinoaryloxide Complexes [J].
Chapman, Andy M. ;
Haddow, Mairi F. ;
Wass, Duncan F. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (45) :18463-18478
[9]   Making plastics from carbon dioxide:: Salen metal complexes as catalysts for the production of polycarbonates from epoxides and CO2 [J].
Darensbourg, Donald J. .
CHEMICAL REVIEWS, 2007, 107 (06) :2388-2410
[10]   Converting carbon dioxide into carbamato derivatives [J].
Dell'Amico, DB ;
Calderazzo, F ;
Labella, L ;
Marchetti, F ;
Pampaloni, G .
CHEMICAL REVIEWS, 2003, 103 (10) :3857-3897
123456