title: Rapid, Reversible, Solid-Gas and Solution-Phase Insertion of CO2 into In-P Bonds.
abstract: The P,P-chelated heteroleptic complex bis[bis(diisopropylphosphino)amido]indium chloride [(i-Pr2P)2N]2InCl was prepared in high yield by treating InCl3 with 2 equiv of (i-Pr2P)2NLi in Et2O/tetrahydrofuran solution. Samples of [(i-Pr2P)2N]2InCl in a pentane slurry, a CH2Cl2 solution, or in the solid state were exposed to CO2, resulting in the insertion of CO2 into two of the four M-P bonds to produce [O2CP(i-Pr2)NP(i-Pr2)]2InCl in each case. Compounds were characterized by multinuclear NMR and IR spectroscopy, as well as single-crystal X-ray diffraction. ReactIR solution studies show that the reaction is complete in less than 1 min at room temperature in solution and in less than 2 h in the solid-gas reaction. The CO2 complex is stable up to at least 60 °C under vacuum, but the starting material is regenerated with concomitant loss of carbon dioxide upon heating above 75 °C. The compound [(i-Pr2P)2N]2InCl also reacts with CS2 to give a complicated mixture of products, one of which was identified as the CS2 cleavage product [S═P(i-Pr2)NP(i-Pr2)]2InCl]2(μ-Cl)[μ-(i-Pr2P)2N)].
authors.affiliation: Department of Chemistry and Chemical Biology, University of New Mexico , Albuquerque, New Mexico 87131, United States.
authors.forename: Diane A
authors.initials: DA
authors.lastname: Dickie
authors.affiliation: Department of Chemistry and Chemical Biology, University of New Mexico , Albuquerque, New Mexico 87131, United States.
authors.forename: Madeline T
authors.initials: MT
authors.lastname: Barker
authors.affiliation: The Atlantic Centre for Green Chemistry, Department of Chemistry, Saint Mary's University , Halifax, Nova Scotia B3H 3C3, Canada.
authors.forename: Michael A
authors.initials: MA
authors.lastname: Land
authors.affiliation: Department of Chemistry and Chemical Biology, University of New Mexico , Albuquerque, New Mexico 87131, United States.
authors.forename: Kira E
authors.initials: KE
authors.lastname: Hughes
authors.affiliation: The Atlantic Centre for Green Chemistry, Department of Chemistry, Saint Mary's University , Halifax, Nova Scotia B3H 3C3, Canada.
authors.forename: Jason A C
authors.initials: JA
authors.lastname: Clyburne
authors.affiliation: Department of Chemistry and Chemical Biology, University of New Mexico , Albuquerque, New Mexico 87131, United States.|Advanced Materials Laboratory, Sandia National Laboratories , Albuquerque, New Mexico 87106, United States.
authors.forename: Richard A
authors.initials: RA
authors.lastname: Kemp