Infrared photodissociation spectroscopic investigation on VO+ and NbO+ hydrolysis catalyzed by water molecules. Issue 1 (16th December 2020)

• Record Type: Journal Article
• Authors: Xin, Ke; Chen, Yinjuan; Zhang, Luning; Xu, Bing; Wang, Xuefeng; Wang, Guanjun
• Is Part Of: Physical chemistry chemical physics. Volume 23:Issue 1(2020)
• Page Start: 528
• Page End: 535
• Publication Date: 2020-12-16
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d0cp04448b
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : We investigate the hydrolysis of vanadium/niobium monoxide cation (VO + /NbO + ) with water molecules in the gas phase. Abstract : We investigate the hydrolysis of vanadium/niobium monoxide cation (VO + /NbO + ) with water molecules in the gas phase. Cationic argon-tagged intermediates, TMO(H2 O) n Ar m + (TM = V, Nb; n = 1–2, m = 1–2), are prepared for examination using infrared photodissociation spectroscopy. The structures of the intermediates are elucidated by comparing them with simulated spectra. VO(H2 O)Ar + or NbO(H2 O)Ar + (for n = 1) is intrinsically a hydrated adduct, represented by H2 O–VOAr + or H2 O–NbOAr +, rather than a dihydroxide, V(OH)2 Ar + or Nb(OH)2 Ar + . However, when a second H2 O molecule is involved (for n = 2), the dihydroxide V(OH)2 (H2 O)Ar + and trihydroxide HNb(OH)3 Ar + are formed. In this process, the six-member cyclic transition state formed by two H2 O molecules markedly reduces the hydrogen transfer energy barrier based on our calculations. This work provides more precise experimental evidence for the Grotthuss-like mechanism proposed in the studies of hydrolysis and tautomerization reactions.