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

Dickie, Diane A.; Barker, Madeline T.; Land, Michael A.; Hughes, Kira E.; Clyburne, Jason A. C.; Kemp, Richard A.

doi:10.1021/acs.inorgchem.5b02031

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

Journal Article · Mon Nov 16 23:00:00 EST 2015 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.5b02031· OSTI ID:1236200

Dickie, Diane A. ^[1]; Barker, Madeline T. ^[1]; Land, Michael A. ^[2]; Hughes, Kira E. ^[1]; Clyburne, Jason A. C. ^[2]; Kemp, Richard A. ^[3]

Univ. of New Mexico, Albuquerque, NM (United States)
Saint Mary's Univ., Halifax, NS (Canada)
Univ. of New Mexico, Albuquerque, NM (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

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)].

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1236200

Report Number(s):: SAND--2015-4422J; 590519

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 23 Vol. 54; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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CCDC 1401832: Experimental Crystal Structure Determination: JUWMAR : bis(bis(Di-isopropylphosphino)amido)-chloro-indium Space Group: P 21/n (14), Cell: a 11.2942(5)Å b 18.3235(8)Å c 15.8967(7)Å, α 90° β 99.0770(10)° γ 90° Dickie, Diane A.; Barker, Madeline T.; Land, Michael A. https://doi.org/10.5517/cc1j1qdp The current record is supplemented by this dataset	dataset	May 2015
CCDC 1401833: Experimental Crystal Structure Determination: JUWMEV : Chloro-bis(1,1,3,3-tetraisopropyl-1λ5-diphosphaz-1-ene-1-carboxylato)-indium(iii) Dickie, Diane; Barker, Madeline; Land, Michael https://doi.org/10.5517/cc1j1qfq The current record is supplemented by this dataset	dataset	May 2015
CCDC 1419352: Experimental Crystal Structure Determination: JUWPOI : (μ2-Chloro)-dichloro-(bis(di-isopropylphosphino)amido)-bis(1,1,3,3-tetraisopropyldiphosphazan-2-ide 1-sulfide)-di-indium Space Group: P 21/c (14), Cell: a 15.1370(6)Å b 20.4781(9)Å c 18.4774(9)Å, α 90° β 111.822(3)° γ 90° Dickie, Diane A.; Barker, Madeline T.; Land, Michael A. https://doi.org/10.5517/cc1jmykn The current record is supplemented by this dataset	dataset	August 2015