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Title: Rapid, reversible, solid–gas and solution-phase insertion of CO2 into In–P bonds

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)].
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:
OSTI Identifier:
1236200
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 Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY