Category Ranking
98%
Total Visits
921
Avg Visit Duration
2 minutes
Citations
20
Article Abstract
We introduce the arsenido ligand onto the Ti ion, yielding a remarkably covalent Ti≡As bond and the parent arsinidene Ti═AsH moiety. An anionic arsenido ligand is assembled via reductive decarbonylation involving the discrete Ti salt [K(cryptand)][(PN)TiCl] () (cryptand = 222-Kryptofix) and Na(OCAs)(dioxane) in thf/toluene to produce the mixed alkali ate-complex [(PN)Ti(As)](μ-KNa(thf)) () and the discrete salt [K(cryptand)][(PN)Ti≡As] () featuring a terminal Ti≡As ligand. Protonation of or with various weak acids cleanly forms the parent arsinidene [(PN)Ti═AsH] (), which upon deprotonation with KCHPh in thf generates the more symmetric anionic arsenido [(PN)Ti(As){μ-K(thf)}] (). Experimental and computational studies suggest the p of to be ∼23, and the bond orders in , , and are all in the range of a Ti≡As triple bond, with decreasing bond order in .
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/jacs.3c12939 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Synthesis and reactivity of a parent phosphathioethynolato-borane and a boraarsaketene.
Chem Sci
May 2025
Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg Am Hubland 97074 Würzburg Germany
We present the synthesis and isolation of the first main-group phosphathioethynolates, [LBH(SCP)] (L = SIMes, CAAC; SIMes = 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene, CAAC = 1-(2,6-diisopropylphenyl)-3,3,5,5-tetramethylpyrrolidin-2-ylidene), in which phosphathioethynolate coordination occurs exclusively through the sulfur atom, giving rise to a phosphaalkyne-type structural motif. This is reflected in the reactivity of the SIMes derivative towards organic azides and [(η-CH)CoCp] (Cp = CH), which mirrors the behavior of 1-adamantylphosphaalkyne, yielding triazaphospholes and a mixed cyclopentadienyl-(1,3-diphosphete) sandwich complex, respectively. Deviations from typical phosphaalkyne reactivity are observed in reactions with boron-containing heterocycles such as pentaphenylborole (PPB) and a carboranyl-substituted 9-borafluorene, which yield an unprecedented bicyclic structure and a zwitterionic spiro compound, respectively.
View Article and Find Full Text PDFSofter Is Better for Titanium: Molecular Titanium Arsenido Anions Featuring Ti≡As Bonding and a Terminal Parent Arsinidene.
J Am Chem Soc
February 2024
Department of Chemistry, University of Pennsylvania, 231 S 34th St, Philadelphia, Pennsylvania 19104, United States.
We introduce the arsenido ligand onto the Ti ion, yielding a remarkably covalent Ti≡As bond and the parent arsinidene Ti═AsH moiety. An anionic arsenido ligand is assembled via reductive decarbonylation involving the discrete Ti salt [K(cryptand)][(PN)TiCl] () (cryptand = 222-Kryptofix) and Na(OCAs)(dioxane) in thf/toluene to produce the mixed alkali ate-complex [(PN)Ti(As)](μ-KNa(thf)) () and the discrete salt [K(cryptand)][(PN)Ti≡As] () featuring a terminal Ti≡As ligand. Protonation of or with various weak acids cleanly forms the parent arsinidene [(PN)Ti═AsH] (), which upon deprotonation with KCHPh in thf generates the more symmetric anionic arsenido [(PN)Ti(As){μ-K(thf)}] ().
View Article and Find Full Text PDFPreparation and Photochemistry of Parent Triplet Vinylarsinidene.
J Am Chem Soc
January 2024
Institute of Organic Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, 35392 Giessen, Germany.
Vinyl pnictinidenes are an elusive family of molecules that have been suggested as key intermediates in multiple chemical reactions and commonly display a predisposition toward open-shell electronic ground states (as is evident from quantum chemical computations). However, owing to their expected extremely high reactivity, no vinyl pnictinidene has ever been isolated and characterized spectroscopically. Here, we report the synthesis and spectroscopic characterization of vinylarsinidene, a higher congener of vinylnitrene.
View Article and Find Full Text PDFTriplet Phenylarsinidene and Its Oxidation to Dioxophenylarsine.
J Am Chem Soc
June 2023
Institute of Organic Chemistry, Justus Liebig University, Giessen 35392, Germany.
Carbenes and nitrenes are key intermediates involved in numerous chemical processes, and they have attracted considerable attention in synthetic chemistry, biochemistry, and materials science. Even though parent arsinidene (H-As) has been characterized well, the high reactivity of subsituted arsinidenes has prohibited their isolation and characterization to date. Here, we report the preparation of triplet phenylarsinidene through the photolysis of phenylarsenic diazide isolated in an argon matrix and its subsequent characterization by infrared and UV/vis spectroscopy.
View Article and Find Full Text PDFActinide Pnictinidene Chemistry: A Terminal Thorium Parent-Arsinidene Complex Stabilised by a Super-Bulky Triamidoamine Ligand.
Angew Chem Int Ed Engl
December 2022
Department of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
We report the direct synthesis of the terminal pnictidenes [An(Tren )(PnH)][M(2,2,2-cryptand)] (Tren ={N(CH CH NSiCy ) } ; An/Pn/M=Th/P/Na 5, Th/As/K 6, U/P/Na 7, U/As/K 8) and their conversion to the pnictides [An(Tren )(PnH )] (An/Pn=Th/P 9, Th/As 10, U/P 11, U/As 12). Use of the super-bulky Tren ligand was essential to accessing complete families, and 6 is an unprecedented example of a terminal thorium-arsinidene complex and only the second structurally authenticated parent terminal arsinidene complex of any metal. Comparison of the terminal Th=AsH unit of 6 to the bridging ThAs(H)K linkage in structurally analogous [Th(Tren ){μ-As(H)K(15-crown-5)}] (Tren ={N(CH CH NSiPr ) } ) reveals a stronger Th-As bond in the former compared to the latter, and a large response overall to the nature of the Th=AsH bonding upon removal of the electrostatically-bound K-ion; the σ-bond changes little but the π-bond is significantly perturbed.
View Article and Find Full Text PDF