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

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)]22-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.

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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://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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