Softer Is Better for Titanium: Molecular Titanium Arsenido Anions Featuring Ti≡As Bonding and a Terminal Parent Arsinidene

Bhunia M, Mohar JS, Sandoval-Pauker C, Fehn D, Yang ES, Gau M, Goicoechea J, Ozarowski A, Krzystek J, Telser J, Meyer K, Mindiola DJ (2024)

Publication Type: Journal article

Publication year: 2024

Journal

Journal of the American Chemical Society American Chemical Society

Book Volume: 146

Pages Range: 3609-3614

Journal Issue: 6

DOI: 10.1021/jacs.3c12939

Abstract

We introduce the arsenido ligand onto the TiIV 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 TiII salt [K(cryptand)][(PN)2TiCl] (1) (cryptand = 222-Kryptofix) and Na(OCAs)(dioxane)1.5 in thf/toluene to produce the mixed alkali ate-complex [(PN)2Ti(As)]2(μ2-KNa(thf)2) (2) and the discrete salt [K(cryptand)][(PN)2Ti≡As] (3) featuring a terminal Ti≡As ligand. Protonation of 2 or 3 with various weak acids cleanly forms the parent arsinidene [(PN)2Ti═AsH] (4), which upon deprotonation with KCH2Ph in thf generates the more symmetric anionic arsenido [(PN)2Ti(As){μ2-K(thf)2}]2 (5). Experimental and computational studies suggest the pKa of 4 to be ∼23, and the bond orders in 2, 3, and 5 are all in the range of a Ti≡As triple bond, with decreasing bond order in 4.

Authors with CRIS profile

Dominik Fehn Lehrstuhl für Anorganische und Allgemeine Chemie Karsten Meyer Lehrstuhl für Anorganische und Allgemeine Chemie

Involved external institutions

University of Pennsylvania US United States (USA) (US) The University of Texas at El Paso US United States (USA) (US) University of Oxford GB United Kingdom (GB) Indiana University US United States (USA) (US) Florida State University (FSU) US United States (USA) (US) Roosevelt University US United States (USA) (US)

How to cite

APA:

Bhunia, M., Mohar, J.S., Sandoval-Pauker, C., Fehn, D., Yang, E.S., Gau, M.,... Mindiola, D.J. (2024). Softer Is Better for Titanium: Molecular Titanium Arsenido Anions Featuring Ti≡As Bonding and a Terminal Parent Arsinidene. Journal of the American Chemical Society, 146(6), 3609-3614. https://dx.doi.org/10.1021/jacs.3c12939

MLA:

Bhunia, Mrinal, et al. "Softer Is Better for Titanium: Molecular Titanium Arsenido Anions Featuring Ti≡As Bonding and a Terminal Parent Arsinidene." Journal of the American Chemical Society 146.6 (2024): 3609-3614.

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