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Functionalization of Carbon Monoxide and tert ‐Butyl Nitrile by Intramolecular Proton Transfer in a Bis(Phosphido) Thorium Complex

Journal Article · · Angewandte Chemie (International Edition)
 [1];  [2];  [1];  [2];  [1]
  1. Department of Chemistry University of Missouri Columbia MO 65211 USA
  2. Universite de Toulouse CNRS INSA, UPS, CNRS, UMR, UMR 5215 LPCNO 135 Avenue de Rangueil 31077 Toulouse France
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Abstract

We report intramolecular proton transfer reactions to functionalize carbon monoxide and tert ‐butyl nitrile from a bis(phosphido) thorium complex. The reaction of (C 5 Me 5 ) 2 Th[PH(Mes)] 2 , Mes=2,4,6‐Me 3 C 6 H 2 , with 1 atm of CO yields (C 5 Me 5 ) 2 Th( κ 2 ‐(O,O)‐OCH 2 PMes‐C(O)PMes), in which one CO molecule is inserted into each thorium–phosphorus bond. Concomitant transfer of two protons, formerly coordinated to phosphorus, are now bound to one of the carbon atoms from one of the inserted CO molecules. DFT calculations were employed to determine the lowest energy pathway. With tert ‐butyl nitrile, t BuCN, only one nitrile inserts into a thorium–phosphorus bond, but the proton is transferred to nitrogen with one phosphido remaining unperturbed affording (C 5 Me 5 ) 2 Th[PH(Mes)][ κ 2 ‐(P,N)‐N(H)C(CMe 3 )P(Mes)]. Surprisingly, reaction of this compound with KN(SiMe 3 ) 2 removes the proton bound to nitrogen, not phosphorus.

Sponsoring Organization:
USDOE
Grant/Contract Number:
NONE; SC0014174
OSTI ID:
1483012
Alternate ID(s):
OSTI ID: 1612101
Journal Information:
Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 51 Vol. 57; ISSN 1433-7851
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

References (82)

Carbon Monoxide and Isocyanide Complexes of Trivalent Uranium Metallocenes journal October 1999
Ein einfacher Weg zum 1-Aza-3-phosphaallyl-System: Struktur eines dimeren Lithium-komplexes und Protonierung zum ersten NH2-substituierten Phosphaalken journal November 1995
Facile Conversion of CO/H2 into Methoxide at a Uranium(III) Center journal June 2011
Triamidoamine-Uranium(IV)-Stabilized Terminal Parent Phosphide and Phosphinidene Complexes journal March 2014
Facile Synthesis of Phosphaamidines and Phosphaamidinates using Nitrilium Ions as an Imine Synthon journal June 2014
Formation of Methane versus Benzene in the Reactions of (C 5 Me 5 ) 2 Th(CH 3 ) 2 with [CH 3 PPh 3 ]X (X=Cl, Br, I) Yielding Thorium-Carbene or Thorium-Ylide Complexes journal September 2017
Actinide-Pnictide (An−Pn) Bonds Spanning Non-Metal, Metalloid, and Metal Combinations (An=U, Th; Pn=P, As, Sb, Bi) journal December 2017
Reaction of B 2 ( o -tol) 4 with CO and Isocyanides: Cleavage of the C≡O Triple Bond and Direct C−H Borylations journal April 2018
Transition-Metal-Like Behavior of Monovalent Boron Compounds: Reduction, Migration, and Complete Cleavage of CO at a Boron Center journal April 2018
A Simple Route to the 1-Aza-3-Phosphaallyl System: Structure of a Dimeric Lithium Complex and Protonation to Give the First NH2-Substituted Phosphaalkene journal November 1995
Facile Conversion of CO/H2 into Methoxide at a Uranium(III) Center journal June 2011
Triamidoamine-Uranium(IV)-Stabilized Terminal Parent Phosphide and Phosphinidene Complexes journal March 2014
Facile Synthesis of Phosphaamidines and Phosphaamidinates using Nitrilium Ions as an Imine Synthon journal June 2014
Formation of Methane versus Benzene in the Reactions of (C 5 Me 5 ) 2 Th(CH 3 ) 2 with [CH 3 PPh 3 ]X (X=Cl, Br, I) Yielding Thorium-Carbene or Thorium-Ylide Complexes journal September 2017
Actinide-Pnictide (An−Pn) Bonds Spanning Non-Metal, Metalloid, and Metal Combinations (An=U, Th; Pn=P, As, Sb, Bi) journal December 2017
Reaction of B 2 ( o -tol) 4 with CO and Isocyanides: Cleavage of the C≡O Triple Bond and Direct C−H Borylations journal April 2018
Transition-Metal-Like Behavior of Monovalent Boron Compounds: Reduction, Migration, and Complete Cleavage of CO at a Boron Center journal April 2018
A Theoretical Study of Uranium(IV) Bis-Methyl Complexes: Towards the Predictive Formation of a Transient Uranium(IV) Carbene Complex journal April 2010
UIII-Induced Reductive Co-Coupling of NO and CO to Form UIV Cyanate and Oxo Derivates journal July 2010
Access to Base Adducts of Low-Valent Organotin-Hydride Compounds by Controlled, Stepwise Hydrogen Abstraction from a Tetravalent Organotin Trihydride journal April 2016
Experimental and Computational Studies on the Formation of Thorium-Copper Heterobimetallics journal August 2016
Metal-Ligand Multiple Bonding in Thorium Phosphorus and Thorium Arsenic Complexes journal November 2017
Short history and present trends of Fischer–Tropsch synthesis journal October 1999
Double insertion of benzophenone into thorium-phosphorus bonds journal February 2018
Sterically encumbered mixed sandwich compounds of uranium(III): Synthesis and reactivity with small molecules journal February 2018
Bis(imino)phosphanes: Synthesis and Coordination Chemistry journal February 2016
Complete Hydrogen Transfer: Tin Hydride Reactivity toward Adamantylisonitrile and Benzonitrile journal May 2018
Mechanisms of carbon monoxide reduction with zirconium hydrides journal April 1980
Proton-Coupled Electron Transfer journal November 2007
Proton-Coupled Electron Transfer journal April 2012
A Combined Theoretical and Experimental Study of the Reaction Products of Laser-Ablated Thorium Atoms with CO:  First Identification of the CThO, CThO - , OThCCO, OTh(η 3 -CCO), and Th(CO) n ( n = 1−6) Molecules journal October 2001
Generation and reactivity of the first mononuclear early metal phosphinidene complex, Cp*2Zr:P(C6H2Me3-2,4,6) journal December 1992
Early actinide alkoxide chemistry. Synthesis, characterization, and molecular structures of thorium(IV) and uranium(IV) aryloxide complexes journal December 1992
Synthesis and Single Crystal X-ray Diffraction Study on the First Isolable Carbonyl Complex of an Actinide, (C5Me4H)3U(CO) journal March 1995
Bonding and coupling of C1 fragments on metal surfaces journal February 1988
Electron-transfer reactions of trivalent uranium. Preparation and structure of the uranium metallocene compounds (MeC5H4)3U:NPh and [(MeC5H4)3U]2[.mu.-.eta.1,.eta.2-PhNCO] journal January 1985
Synthesis and reactivity of cyclopentadienylhafnium phosphido complexes. Hydrogenolysis and carbon monoxide insertion for Hf-PR2 bonds journal August 1985
Organoactinide carbonylation and carboxylation chemistry. Structural electronic, bond energy, and photochemical effects on migratory insertion in the tris(cyclopentadienyl)thorium hydrocarbyl series journal June 1984
Carbon monoxide activation by organoactinides. .eta.2-Acyl-carbon monoxide coupling and the formation of metal-bound ketenes journal August 1983
Carbon monoxide activation by organoactinides. Migratory carbon monoxide insertion into metal-hydrogen bonds to produce mononuclear formyls journal November 1981
Bis(pentamethylcyclopentadienyl)actinide alkyls: facile activation of carbon monoxide, carbon-carbon double bond formation, and the production of unusual oxygen-bonded migratory insertion products journal October 1978
Carbon monoxide activation by f-element organometallics. An unusually distorted, carbenelike dihaptoacyl and CO tetramerization journal July 1980
Hard and Soft Acids and Bases journal November 1963
Noble Gas−Actinide Complexes of the CUO Molecule with Multiple Ar, Kr, and Xe Atoms in Noble-Gas Matrices journal March 2003
Comparative Reactivity of Sterically Crowded nf 3 (C 5 Me 5 ) 3 Nd and (C 5 Me 5 ) 3 U Complexes with CO:  Formation of a Nonclassical Carbonium Ion versus an f Element Metal Carbonyl Complex journal November 2003
Hydrogenation of Carbon Monoxide by Tetranuclear Rare Earth Metal Polyhydrido Complexes. Selective Formation of Ethylene and Isolation of Well-Defined Polyoxo Rare Earth Metal Clusters journal June 2006
Reductive Cyclotetramerization of CO to Squarate by a U(III) Complex:  The X-ray Crystal Structure of [(U (η-C 8 H 6 {Si i Pr 3 -1,4} 2 )(η-C 5 Me 4 H)] 2 (μ-η 2 : η 2 -C 4 O 4 ) journal August 2006
Trivalent [(C 5 Me 5 ) 2 (THF)Ln] 2 (μ - η 2 :η 2 -N 2 ) Complexes as Reducing Agents Including the Reductive Homologation of CO to a Ketene Carboxylate, (μ-η 4 -O 2 CCCO) 2 - journal November 2006
Reactions of Monomeric [1,2,4-(Me 3 C) 3 C 5 H 2 ] 2 CeH and CO with or without H 2 :  An Experimental and Computational Study journal March 2007
Systematic Studies of Early Actinide Complexes:  Thorium(IV) Fluoroketimides journal April 2007
Homogeneous CO Hydrogenation: Dihydrogen Activation Involves a Frustrated Lewis Pair Instead of a Platinum Complex journal March 2010
Small Molecule Activation by Uranium Tris(aryloxides): Experimental and Computational Studies of Binding of N 2 , Coupling of CO, and Deoxygenation Insertion of CO 2 under Ambient Conditions journal June 2011
Versatile Reactivity of a Four-Coordinate Scandium Phosphinidene Complex: Reduction, Addition, and CO Activation Reactions journal September 2013
Mechanistic Studies on the Reductive Cyclooligomerisation of CO by U(III) Mixed Sandwich Complexes; the Molecular Structure of [(U(η-C 8 H 6 {Si i Pr 3 -1,4} 2 )(η-Cp*)] 2 (μ-η 1 :η 1 -C 2 O 2 ) journal October 2008
Synthesis and Reaction of [(Tp i Pr 2 )LnH 2 ] 3 (Ln = Y, Lu) with CO: Trinuclear Cluster-Bound Propenolate en Route to Selective Formation of Propene journal January 2010
Reaction of Laser-Ablated Uranium Atoms with CO:  Infrared Spectra of the CUO, CUO - , OUCCO, (η 2 -C 2 )UO 2 , and U(CO) x ( x = 1−6) Molecules in Solid Neon journal October 1999
Formation of a Bridging Phosphinidene Thorium Complex journal November 2015
Synthesis, Structure, and Reactivity of the Sterically Crowded Th 3+ Complex (C 5 Me 5 ) 3 Th Including Formation of the Thorium Carbonyl, [(C 5 Me 5 ) 3 Th(CO)][BPh 4 ] journal February 2017
CO Reduction to CH 3 OSiMe 3 : Electrophile-Promoted Hydride Migration at a Single Fe Site journal February 2017
Cooperative Trimerization of Carbon Monoxide by Lithium and Samarium Boryls journal November 2017
Homoleptic Actinide Complexes with Chelating Diphosphinophosphido Ligands: New Mode of Reactivity with Carbon Monoxide and the X-ray Crystal Structure of U{P(CH2CH2PMe2)2}4 journal August 1995
Carbon monoxide activation by organoactinides. Formyl pathways in CO homologation and hydrogenation journal December 1982
Homogeneous CO Hydrogenation: Ligand Effects on the Lewis Acid-Assisted Reductive Coupling of Carbon Monoxide journal October 2010
Synthesis, Structure, and Reactivity of a Thorium Metallocene Containing a 2,2′-Bipyridyl Ligand journal January 2012
Steric Effects in the Reductive Coupling of CO by Mixed-Sandwich Uranium(III) Complexes journal December 2012
Insertion of Carbodiimides and Organic Azides into Actinide−Carbon Bonds journal June 2009
Nitrogen reduction and functionalization by a multimetallic uranium nitride complex journal July 2017
Carbon oxygenate transformations by actinide compounds and catalysts journal January 2017
Carbon monoxide coupling and functionalisation at a simple uranium coordination complex journal January 2011
Formation of cyanates in low-valent uranium chemistry: a synergistic experimental/theoretical study journal January 2014
Hydrogen abstraction from organotin di- and trihydrides by N-heterocyclic carbenes: a new method for the preparation of NHC adducts to tin( ii ) species and observation of an isomer of a hexastannabenzene derivative [R 6 Sn 6 ] journal January 2014
Insertion of t BuNC into thorium–phosphorus and thorium–arsenic bonds: phosphaazaallene and arsaazaallene moieties in f element chemistry journal January 2016
Insertion, protonolysis and photolysis reactivity of a thorium monoalkyl amidinate complex journal January 2018
A P–H functionalized Al/P-based frustrated Lewis pair – hydrophosphination of nitriles, ring opening with cyclopropenones and evidence of PC double bond formation journal January 2018
Azaphosphaallyl anion lithium [ArNC(But)PAr]−Li+(THF)4 and its monomeric potassium and thallium complexes (Ar = 2, 6-iPr2C6H3) journal January 2009
A DFT study of the reactivity of actinidocenes (U, Np and Pu) with pyridine and pyridine N-oxide derivatives journal January 2010
Uranium-mediated activation of small molecules journal January 2011
Reductive coupling of carbon monoxide by U(iii) complexes—a computational study journal January 2011
Computational insight into the reductive oligomerisation of CO at uranium(iii) mixed-sandwich complexes journal January 2012
Direct conversion of carbon monoxide to a coordinated secondary alcohol derivative by a thorium phosphido complex journal January 1994
Homologation and functionalization of carbon monoxide by a recyclable uranium complex journal May 2012
Reductive Cyclotrimerization of Carbon Monoxide to the Deltate Dianion by an Organometallic Uranium Complex journal February 2006

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