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

Journal Article · · Inorganic Chemistry
 [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)
+ Show Author Affiliations
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)].
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

References (53)

Aktivierung von Schwefelkohlenstoff an Trirutheniumclustern: Synthese und Kristallstruktur von [Ru3(CO)5(μ-H)2(μ-PCy2)(μ-Ph2PCH2PPh2){μ-η2-PCy2C(S)}(μ3-S)] und [Ru3(CO)5(CS)(μ-H)(μ-PtBu2)(μ-PCy2)2(μ3-S)] journal December 2001
Reversible Metal-Free Carbon Dioxide Binding by Frustrated Lewis Pairs journal August 2009
Geminal Phosphorus/Aluminum-Based Frustrated Lewis Pairs: CH versus CC Activation and CO 2 Fixation journal March 2011
Stoichiometric Reduction of CO2 to CO by Aluminum-Based Frustrated Lewis Pairs journal July 2011
Frustrated Lewis Pair Inspired Carbon Dioxide Reduction by a Ruthenium Tris(aminophosphine) Complex journal October 2012
1,1-Carbozirconation: Unusual Reaction of an Alkyne with a Methyl Zirconocene Cation and Subsequent Frustrated Lewis Pair Like Reactivity journal November 2013
Frustrated Lewis Pair Chemistry: Development and Perspectives journal May 2015
Beiträge zur Chemie des Bors, 219. (Di-tert-butylphosphanylimino)(2,2,6,6-tetramethylpiperidino)boran: ein BNP-1,3-”Dipol” journal September 1993
CO2 and Formate Complexes of Phosphine/Borane Frustrated Lewis Pairs journal July 2011
Enhanced Photocatalytic Reduction of CO 2 to CO through TiO 2 Passivation of InP in Ionic Liquids journal July 2015
Synthesis and Reactivity of New Bis(tetramethylpiperidino)(phosphanyl)alumanes journal September 2007
Reactions of CS2 and C(S)NPh Adducts of N-Heterocyclic Carbenes with [Ru3(CO)12]: Remarkable Reactivity of These Betaines Involving One or Two C-S Bond Activation Processes journal April 2012
Experimental and Theoretical Investigations of CO 2 Sorption by a 3D In-MOF with Multiple 1D Channels: CO 2 Sorption by a 3D In-MOF with Multiple 1D Channels journal July 2015
Synthese und Charakterisierung neuer intramolekular phosphorstabilisierter Aluminium-, Gallium- und Indiumorganyle journal October 2007
Insertion reactions of CO2, OCS, and CS2 into the Sn–N bonds of (Me2N)2Sn: NMR and X-ray structural characterization of the products journal October 2011
Activation of CO2 and CS2 by (Me3Si)(i-Pr2P)NH and its zinc complex journal July 2013
Formation of a Stable Complex, RuCl 2 (S 2 CPPh 3 )(PPh 3 ) 2 , Containing an Unstable Zwitterion from the Reaction of RuCl 2 (PPh 3 ) 3 with Carbon Disulfide journal April 2015
Transition-metal thiocarbonyls and selenocarbonyls journal October 1977
Phosphinecarboxylate ligands formed by the insertion of carbon dioxide into metal-phosphido bonds. Preparation and structural characterization of tetrakis(di-tert-butylphosphinecarboxylato)dimolybdenum journal September 1987
Carbon−Sulfur Bond Cleavage in Bis( N -alkyldithiocarbamato)cadmium(II) Complexes:  Heterolytic Desulfurization Coupled to Topochemical Proton Transfer journal May 2004
Reactivity of Bis(2,2,5,5-tetramethyl-2,5-disila-1-azacyclopent-1-yl)tin with CO 2 , OCS, and CS 2 and Comparison to That of Bis[bis(trimethylsilyl)amido]tin journal December 2010
Photocatalytic Splitting of CS 2 to S 8 and a Carbon–Sulfur Polymer Catalyzed by a Bimetallic Ruthenium(II) Compound with a Tertiary Amine Binding Site: Toward Photocatalytic Splitting of CO 2 ? journal November 2011
Formation of a Reversible, Intramolecular Main-Group Metal–CO 2 Adduct journal November 2011
NH/PH Isomerization and a Lewis Pair for Carbon Dioxide Capture journal July 2013
Toward Solar-Driven Photocatalytic CO 2 Reduction Using Water as an Electron Donor journal February 2015
Synthesis, Structures, and Multinuclear NMR Spectra of Tin(II) and Lead(II) Complexes of Tellurium-Containing Imidodiphosphinate Ligands: Preparation of Two Morphologies of Phase-Pure PbTe from a Single-Source Precursor journal December 2009
Reactions involving carbon dioxide and mixed amido-phosphido dinuclear compounds. M2(NMe2)4(PR2)2(M.tplbond.M), where M = Mo and W. Comparative study of the insertion of carbon dioxide into metal-nitrogen and metal-phosphorus bonds journal October 1989
Preorganized Frustrated Lewis Pairs journal December 2011
Reactions of a Cationic Geminal Zr + /P Pair with Small Molecules journal April 2013
Noninteracting, Vicinal Frustrated P/B-Lewis Pair at the Norbornane Framework: Synthesis, Characterization, and Reactions journal June 2013
Quest for Anionic MOF Membranes: Continuous sod -ZMOF Membrane with CO 2 Adsorption-Driven Selectivity journal January 2015
Activation of CS 2 and CS by ML 3 Complexes journal August 2008
Room Temperature Reduction of CO 2 to Methanol by Al-Based Frustrated Lewis Pairs and Ammonia Borane journal February 2010
Reactions of Modified Intermolecular Frustrated P/B Lewis Pairs with Dihydrogen, Ethene, and Carbon Dioxide journal January 2012
Stoichiometric Reduction of CO 2 to CO by Phosphine/AlX 3 -Based Frustrated Lewis Pairs journal July 2013
CO 2 Activation with Bulky Neutral and Cationic Phenoxyalanes journal July 2013
Structures and CO 2 Reactivity of Zinc Complexes of Bis(diisopropyl-) and Bis(diphenylphosphino)amines journal November 2014
Elucidation of Heterocumulene Activation by a Nucleophilic-at-Metal Iridium(I) Carbene journal November 2008
Structurally simple complexes of CO 2 journal January 2015
Activation of carbon dioxide by new mixed sandwich uranium( iii ) complexes incorporating cyclooctatetraenyl and pyrrolide, phospholide, or arsolide ligands journal January 2015
Two stable 3D porous metal–organic frameworks with high performance for gas adsorption and separation journal January 2015
Complete disassembly of carbon disulfide by a ditantalum complex journal January 2009
Bis-boranes in the frustrated Lewis pair activation of carbon dioxide journal January 2011
Stoichiometric CO2 reductions using a bis-borane-based frustrated Lewis pair journal January 2012
Silyl-migrations in frustrated Lewis pair chemistry: reactions of ((CH3)3Si)3P and B(C6F4H)3 with H2 and CO2 journal January 2012
Dimeric aluminum–phosphorus compounds as masked frustrated Lewis pairs for small molecule activation journal January 2012
Exchange chemistry of tBu3P(CO2)B(C6F5)2Cl journal January 2012
Activation of CO2 by phosphinoamide hafnium complexes journal January 2013
CO2 reduction via aluminum complexes of ammonia boranes journal January 2013
Reactions of dimethylzirconocene complexes with a vicinal frustrated P/B Lewis pair journal January 2013
Low-valent Iron Complexes Stabilised by a Bulky Guanidinate Ligand: Synthesis and Reactivity Studies journal January 2014
Zwitterionic CS2 Adducts of Bis(dialkylphosphino)amines: Syntheses, Spectroscopy, and Structures journal January 2015
The Cambridge Structural Database: a quarter of a million crystal structures and rising journal May 2002

Cited By (2)

Stoichiometric Reactions of CO 2 and Indium-Silylamides and Catalytic Synthesis of Ureas journal October 2017
Heavy Metals Make a Chain: A Catenated Bismuth Compound journal May 2020

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY