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Title: Rapid, reversible, solid–gas and solution-phase insertion of CO 2 into In–P bonds

The P,P-chelated heteroleptic complex bis[bis(diisopropylphosphino)amido]indium chloride [(i-Pr 2P) 2N] 2InCl was prepared in high yield by treating InCl 3 with 2 equiv of (i-Pr 2P) 2NLi in Et 2O/tetrahydrofuran solution. Samples of [(i-Pr 2P) 2N] 2InCl in a pentane slurry, a CH 2Cl 2 solution, or in the solid state were exposed to CO 2, resulting in the insertion of CO 2 into two of the four M–P bonds to produce [O 2CP(i-Pr 2)NP(i-Pr 2)] 2InCl in each case. These 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 CO 2 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. Furthermore, the compound [(i-Pr 2P) 2N] 2InCl also reacts with CS 2 to give a complicated mixture of products, one of which was identified as the CS 2 cleavage product [S=P(i-Pr 2)NP(i-Pr 2)] 2InCl] 2(μ-Cl)[μ-(i-Pr 2P) 2N)].
Authors:
 [1] ;  [1] ;  [2] ;  [1] ;  [2] ;  [3]
  1. Univ. of New Mexico, Albuquerque, NM (United States)
  2. Saint Mary's Univ., Halifax, NS (Canada)
  3. Univ. of New Mexico, Albuquerque, NM (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Report Number(s):
SAND-2015-4422J
Journal ID: ISSN 0020-1669; 590519
Grant/Contract Number:
AC04-94AL85000
Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 54; Journal Issue: 23; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Research Org:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1236200

Dickie, Diane A., Barker, Madeline T., Land, Michael A., Hughes, Kira E., Clyburne, Jason A. C., and Kemp, Richard A.. Rapid, reversible, solid–gas and solution-phase insertion of CO2 into In–P bonds. United States: N. p., Web. doi:10.1021/acs.inorgchem.5b02031.
Dickie, Diane A., Barker, Madeline T., Land, Michael A., Hughes, Kira E., Clyburne, Jason A. C., & Kemp, Richard A.. Rapid, reversible, solid–gas and solution-phase insertion of CO2 into In–P bonds. United States. doi:10.1021/acs.inorgchem.5b02031.
Dickie, Diane A., Barker, Madeline T., Land, Michael A., Hughes, Kira E., Clyburne, Jason A. C., and Kemp, Richard A.. 2015. "Rapid, reversible, solid–gas and solution-phase insertion of CO2 into In–P bonds". United States. doi:10.1021/acs.inorgchem.5b02031. https://www.osti.gov/servlets/purl/1236200.
@article{osti_1236200,
title = {Rapid, reversible, solid–gas and solution-phase insertion of CO2 into In–P bonds},
author = {Dickie, Diane A. and Barker, Madeline T. and Land, Michael A. and Hughes, Kira E. and Clyburne, Jason A. C. and Kemp, Richard A.},
abstractNote = {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. These 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. Furthermore, 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)].},
doi = {10.1021/acs.inorgchem.5b02031},
journal = {Inorganic Chemistry},
number = 23,
volume = 54,
place = {United States},
year = {2015},
month = {11}
}