Softer Is Better for Titanium: Molecular Titanium Arsenido Anions Featuring Ti≡As Bonding and a Terminal Parent Arsinidene.
J Am Chem Soc
; 146(6): 3609-3614, 2024 Feb 14.
Article
em En
| MEDLINE
| ID: mdl-38290427
ABSTRACT
We introduce the arsenido ligand onto the TiIV ion, yielding a remarkably covalent Ti≡As bond and the parent arsinidene TiâAsH 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)2TiâAsH] (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 â¼23, 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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Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
J Am Chem Soc
Ano de publicação:
2024
Tipo de documento:
Article
País de afiliação:
Estados Unidos