skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Phosphorus-Atom Transfer from Phosphaethynolate to an Alkylidyne

Journal Article · · Angewandte Chemie
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
  2. Inst. for Basic Science (IBS) Daejeon (South Korea). Center for Catalytic Hydrocarbon Functionalizations; Korea Advanced Inst. Science and Technology (KAIST), Daejeon (South Korea)
  3. Inst. for Basic Science (IBS) Daejeon (South Korea). Center for Catalytic Hydrocarbon Functionalizations
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
+ Show Author Affiliations

A low-spin and mononuclear vanadium complex, (Menacnac)V(CO)(η2-P≡CtBu) (2) (Menacnac-=[ArNC(CH3)]2CH, Ar=2,6-iPr2C6H3), was prepared upon treatment of the vanadium neopentylidyne complex (Menacnac)V≡CtBu(OTf) (1) with Na(OCP)(diox)2.5 (diox=1,4-dioxane), while the isoelectronic ate-complex [Na(15-crown-5)]{([ArNC(CH2)]CH[C(CH3)NAr])V(CO)(η2-P≡CtBu)} (4), was obtained via the reaction of Na(OCP)(diox)2.5 and ([ArNC(CH2)]CH[C(CH3)NAr])V≡CtBu(OEt2) (3) in the presence of crown-ether. Computational studies suggest that the P-atom transfer proceeds by [2+2]-cycloaddition of the P≡C bond across the V≡CtBu moiety, followed by a reductive decarbonylation to form the V-C≡O linkage. Additionally, the nature of the electronic ground state in diamagnetic complexes, 2 and 4, was further investigated both theoretically and experimentally, using a combination of density functional theory (DFT) calculations, UV/Vis and NMR spectroscopies, cyclic voltammetry, X-ray absorption spectroscopy (XAS) measurements, and comparison of salient bond metrics derived from X-ray single-crystal structural characterization. In combination, these data are consistent with a low-valent vanadium ion in complexes 2 and 4. This study represents the first example of a metathesis reaction between the P-atom of [PCO]- and an alkylidyne ligand.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
National Science Foundation (NSF); National Institutes of Health (NIH); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC02-06CH11357; CHE-0848248; CHE-1152123; 3R01GM118510-03S1; 3R01GM087605-06S1
OSTI ID:
1845329
Journal Information:
Angewandte Chemie, Vol. 133, Issue 46; ISSN 0044-8249
Publisher:
German Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (85)

Tetra-tert-butyltetraphosphacubane: The First Thermal Cyclooligomerization of a Phosphaalkyne journal August 1989
(Phosphanyl)phosphaketenes as building blocks for novel phosphorus heterocycles journal January 2017
Terminal Vanadium−Neopentylidyne Complexes and Intramolecular Cross-Metathesis Reactions to Generate Azametalacyclohexatrienes journal August 2004
The 2-Phosphaethynolate Anion: A Convenient Synthesis and [2+2] Cycloaddition Chemistry journal August 2013
Phosphanierung von Kohlenmonoxid: eine einfache Synthese von Natriumphosphaethinolat (NaOCP) journal July 2011
Phosphideinbau in ein Cyclotrisilen journal November 2014
A Stable Heterocyclic Amino(phosphanylidene‐σ 4 ‐phosphorane) Germylene journal March 2016
Sodium Phosphaethynolate as a Building Block for Heterocycles journal January 2014
Coordination chemistry of trimethylsilylphosphaalkyne: a phosphaalkyne bearing a reactive substituent journal January 2012
The microwave spectrum of 1-phosphapropyne, CH3CP journal August 1979
Coulomb repulsion versus cycloaddition: formation of anionic four-membered rings from sodium phosphaethynolate, Na(OCP) journal January 2014
A “Push–Pull” Stabilized Phosphinidene Supported by a Phosphine‐Functionalized β‐Diketiminato Ligand journal July 2020
Limitations of Steric Bulk: Towards Phospha‐germynes and Phospha‐stannynes journal April 2018
Phosphorus and Arsenic Atom Transfer to Isocyanides to Form π‐Backbonding Cyanophosphide and Cyanoarsenide Titanium Complexes journal June 2021
From a Phosphaketenyl-Functionalized Germylene to 1,3-Digerma-2,4-diphosphacyclobutadiene journal March 2016
The phosphaethynolate anion reacts with unsaturated bonds: DFT investigations into [2+2], [3+2] and [4+2] cycloadditions journal January 2014
K -edge absorption spectra of selected vanadium compounds journal November 1984
Understanding chemical shielding tensors using group theory, MO analysis, and modern density-functional theory journal March 2009
N‐Heterocyclic Carbenes as Promotors for the Rearrangement of Phosphaketenes to Phosphaheteroallenes: A Case Study for OCP to OPC Constitutional Isomerism journal April 2016
Cyclo-oligomerization of isocyanates with Na(PH 2 ) or Na(OCP) as “P − ” anion sources journal January 2015
A spectroscopic study of HCP, the phosphorus analogue of hydrocyanic acid journal April 1969
Salen supported Al–O–CP and Ga–PCO complexes journal January 2019
Is the phosphaethynolate anion, (OCP)−, an ambident nucleophile? A spectroscopic and computational study journal January 2014
The Rise of Phosphaethynolate Chemistry in Early Transition Metals, Actinides, and Rare‐Earth Complexes journal October 2019
Oxidative Coupling of Terminal Rhenium Pnictide Complexes journal June 2019
Elements of Molecular and Biomolecular Electrochemistry book January 2006
Hcp, a Unique Phosphorus Compound journal April 1961
N‐Heterocyclic Carbenes as Promotors for the Rearrangement of Phosphaketenes to Phosphaheteroallenes: A Case Study for OCP to OPC Constitutional Isomerism journal April 2016
Phosphination of Carbon Monoxide: A Simple Synthesis of Sodium Phosphaethynolate (NaOCP) journal July 2011
Phosphaalkine – Synthesen, Reaktionen, Koordinationsverhalten journal November 1988
Small molecule activation by boron-containing heterocycles journal January 2019
From a Phosphaketenyl-Functionalized Germylene to 1,3-Digerma-2,4-diphosphacyclobutadiene journal March 2016
Phosphaalkynes—Syntheses, Reactions, Coordination Behavior[New Synthetic Methods(73)] journal November 1988
β-Diiminato Complexes of VIII and TiIII – Formation and Structure of Stable Paramagnetic Dialkylmetal Compounds journal October 1998
Isolation of Au-, Co-η 1 PCO and Cu-η 2 PCO complexes, conversion of an Ir–η 1 PCO complex into a dimetalladiphosphene, and an interaction-free PCO anion journal January 2016
Zwitterionic and Cationic Titanium and Vanadium Complexes Having Terminal M−C Multiple Bonds. The Role of the β-Diketiminate Ligand in Formation of Charge-Separated Species journal June 2009
Oligomerization of phosphaalkynes mediated by bulky N-heterocyclic carbenes: avenues to novel phosphorus frameworks journal January 2019
Synthesis of Azaphosphinines by Directed Inverse‐Electron‐Demand Hetero‐Diels–Alder Reactions with Na(OCP) journal July 2018
2,4,6‐Tri(hydroxy)‐1,3,5‐triphosphinine, P 3 C 3 (OH) 3 : The Phosphorus Analogue of Cyanuric Acid journal December 2016
The Chemistry of the 2-Phosphaethynolate Anion journal November 2018
A Singlet Phosphinidene Stable at Room Temperature journal July 2016
Ein neues Hexamer vontBuCP: Synthese, Struktur und theoretische Untersuchungen journal November 1994
Sodium phosphaethynolate, Na(OCP), as a “P” transfer reagent for the synthesis of N-heterocyclic carbene supported P 3 and PAsP radicals journal January 2014
A Convenient Synthesis of 1,2,4- and 1,3,4-Azadiphospholes journal August 2016
A substituent-tolerant synthetic approach to N/P-“loaded” heteroarenes journal January 2018
Oxidative Coupling of Terminal Rhenium Pnictide Complexes journal August 2019
Highly Reactive Scandium Phosphinoalkylidene Complex: C–H and H–H Bonds Activation journal January 2017
Synthese und Reaktivität von Nickel-stabilisierten μ 2 :η 2 ,η 2 -P 2 -, As 2 - und PAs-Einheiten journal December 2017
The First Example of the Two-Electron Reduction of a Phosphaalkyne - Synthesis and Structural Characterisation of the Diuranium(IV) Pentalene Complex [(U{η 5 -C 5 Me 5 }{η 8 -C 8 H 4 (Si i Pr 3 -1,4) 2 }) 2 (μ-η 2 :η 1 - t BuCP)] journal May 2013
The Structures and Energies of Phosphaalkyne Trimers, (HCP) 3 journal November 1999
Magnetic Shielding of Nuclei in Molecules journal June 1950
Tetraphosphasemibullvalen: erste Valenzisomerisierungen im Phosphaalkin-Cyclotetramer-System journal June 1997
Terminal tungsten pnictide complex formation through pnictaethynolate decarbonylation journal January 2017
The heterocubane [TerSnAs] 4 journal January 2018
Synthetic and Spectroscopic Investigations Enabled by Modular Synthesis of Molecular Phosphaalkyne Precursors journal November 2018
2,4,6-Tri(hydroxy)-1,3,5-triphosphinine, P 3 C 3 (OH) 3 : The Phosphorus Analogue of Cyanuric Acid journal December 2016
Molecular and crystal structure oftert-butylphosphaethyne journal December 1991
Theory and computation of nuclear magnetic resonance parameters journal January 2007
Synthesis and Reactivity of the Phosphorus Analogues of Cyclopentadienone, Tricyclopentanone, and Housene journal January 2018
Annulated 1,3,4-Azadiphospholides: Heterocycles with Widely Tunable Optical Properties journal August 2017
Phosphaketenes as Building Blocks for the Synthesis of Triphospha Heterocycles journal July 2014
Main group and transition metal-mediated phosphaalkyne oligomerizations journal July 2014
Die Chemie des 2-Phosphaethinolat-Anions journal November 2018
Synthesis and Reactivity of Nickel-Stabilised μ 2 :η 2 ,η 2 -P 2 , As 2 and PAs Units journal December 2017
Taming a silyldiium cation and its reactivity towards sodium phosphaethynolate journal January 2018
Rearrangement of bis(alkylidynyl)phosphines to phospha-acyls journal January 2017
A stable phosphanyl phosphaketene and its reactivity journal January 2015
The 2-Phosphaethynolate Anion: A Convenient Synthesis and [2+2] Cycloaddition Chemistry journal August 2013
Experimental and theoretical correlations between vanadium K-edge X-ray absorption and K $$\varvec{\beta} $$ β emission spectra journal June 2016
Tetra-tert-butyl-tetraphosphacuban-die erste thermische Cyclooligomerisierung eines Phosphaalkins journal August 1989
Synthesis of P 2 C 2 O 2 and P 2 CO via NHC-mediated coupling of the phosphaethynolate anion journal January 2017
A Planar Ti 2 P 2 Core Assembled by Reductive Decarbonylation of − O−C≡P and P−P Radical Coupling journal April 2017
Sodium Phosphaethynolate as a Building Block for Heterocycles journal January 2014
η 2 -Coordination of a Phosphaalkyne to an Amino Olefin Nickel Complex and Regioselective Catalyzed Cyclooligomerization to Dewar 1,3,5-Triphosphabenzene : Phosphaalkyne Coordination to an Amino Olefin Ni Complex journal October 2013
Spectroscopic Characterization, Computational Investigation, and Comparisons of ECX – (E = As, P, and N; X = S and O) Anions journal June 2017
Stabilizing P≡P: P22–, P2⋅–, and P20 as bridging ligands journal July 2021
Formation of a Uranium-Bound η 1 -Cyaphide (CP – ) Ligand via Activation and C–O Bond Cleavage of Phosphaethynolate (OCP – ) journal October 2017
A Stable Heterocyclic Amino(phosphanylidene-σ 4 -phosphorane) Germylene journal March 2016
Diverse Bonding Activations in the Reactivity of a Pentaphenylborole toward Sodium Phosphaethynolate: Heterocycle Synthesis and Mechanistic Studies journal March 2017
Phosphorus and Arsenic Atom Transfer to Isocyanides to Form π‐Backbonding Cyanophosphide and Cyanoarsenide Titanium Complexes journal June 2021
Insertion of sodium phosphaethynolate, Na[OCP], into a zirconium–benzyne complex journal January 2017
Phosphide Delivery to a Cyclotrisilene journal November 2014
η2-tert-Butylphosphaacetylen-Komplexe des Titanocens und Zirkonocens journal August 1990
Annulated 1,3,4-Azadiphospholides: Heterocycles with Widely Tunable Optical Properties journal August 2017
Synthesis and Reactivity of the Phosphorus Analogues of Cyclopentadienone, Tricyclopentanone, and Housene journal January 2018

Linked Research (2)

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
diketeiminate
phosphaalkyne
phosphaethynolate
phosphorus
vanadium
alkylidyne