Structures and CO2 Reactivity of Zinc Complexes of Bis(diisopropyl-) and Bis(diphenylphosphino)amines

被引：17
|
作者：
Dickie, Diane A. [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：
ORGANOMETALLICS | 2014年 / 33卷 / 22期
基金：
美国国家科学基金会; 加拿大自然科学与工程研究理事会; 美国能源部;
关键词：
FRUSTRATED LEWIS PAIRS; POLYFUNCTIONAL MOLECULES; CARBON-DIOXIDE; CRYSTAL-STRUCTURES; PHOSPHAZENE ANION; CHEMISTRY; REDUCTION; LIGANDS; CATALYSIS;
D O I：
10.1021/om500856p
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The bis(phosphino)amines (R2P)NH(PR'(2)) (R = R' = isopropyl; R = R' = phenyl; R = isopropyl, R' = phenyl) react with ZnEt2 to form complexes with two different structural motifs, either the homoleptic monomeric P,P-chelates Zn[N(i-Pr2P)(2)](2) and Zn[N(i-Pr2P)(Ph2P)](2) or the heteroleptic dimeric Zn2N2P2 heterocycles {EtZn[N(PPh2)(2)]}(2) and {EtZn[N(PPh2)(i-Pr2P)]}(2). In two cases, CO2 reacts with these complexes to give adducts Zn[O2CP(i-Pr-2)NP(i-Pr-2)](2) and Zn[O2CP(i-Pr-2)NPPh2][Ph2PN(i-Pr2P)]ZnEt2, similar to adducts formed from the reaction of CO2 with frustrated Lewis pairs (FLPs). In the other two cases, reaction with CO2 results in cleavage and rearrangement of the NP bonds to give either N(PPh2)(3) or Ph2P(iPr(2)P)NPPh2. The zinc complexes and their CO2 products were characterized with a combination of single crystal X-ray diffraction and multinuclear NMR spectroscopy.
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页码：6511 / 6518
页数：8
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