Synthesis, characterization and reactions of [RhCl(CO){(Ph2P(CH2CH2O)m CH2CH2Ph2-P,P′)}]n (m=3, 4, 5 n=1, 2...) metallacrown crown ethers

被引：0
|
作者：
Smith, Dale C. [1 ]
Cagle, Ethan C. [2 ]
Gray, Gary M. [2 ]
机构：
[1] Avanti Polar Lipids, Alabaster, AL USA
[2] Univ Alabama Birmingham, Dept Chem, Birmingham, AL 35294 USA
来源：
JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2018年 / 876卷
关键词：
RAY CRYSTAL-STRUCTURES; COORDINATED CARBON-MONOXIDE; GROUP-6; METAL-CARBONYLS; RHODIUM PHOSPHINOETHER COMPLEXES; CHELATING PHOSPHINITE COMPLEXES; TRANS ISOMERIZATION EQUILIBRIA; CATION-BINDING; BIS(PHOSPHITE) LIGANDS; MOLECULAR-STRUCTURES; PHOSPHORUS-DONOR;
D O I：
10.1016/j.jorganchem.2018.09.004
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The reactions of [RhCl(cod)](2) and Ph2P(CH2CH2O)(n)CH2CH2PPh2P (n = 3, 4, 5) under a CO atmosphere yield [RhCl(CO){(Ph2P(CH2CH2O)(n) CH2CH2Ph2 P,P')}](m) monocarbonyl metallacrown ethers. These complexes are mixtures of cyclic n-mers and monomers with trans coordination geometries at the rhodium. The monocarbonyl rhodium metallacrown ethers reversibly react with CO at atmospheric pressure to form [RhCl(CO)(2){(Ph2P(CH2CH2O)(n)CH2CH2Ph2-P,P')}](m) dicarbonyl metallacrown ethers. These complexes are only stable under a CO atmosphere as demonstrated by P-31{H-1} NMR spectroscopy. Upon prolonged exposure to the atmosphere, all the monocarbonyl metallacrown ethers lose CO and undergo phosphine ligand oxidation to form [RhCl(H2O){Ph2P(O)(CH2CH2O)(n)CH2CH2P(O)Ph-2-O,O'}] metallacrown ethers. These are the first examples of metallacrown ethers in which the transition metal is coordinated via phosphine oxide donors. (C) 2018 Elsevier B.V. All rights reserved.
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页码：78 / 82
页数：5
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