NDLI: Kinetics of protonation of tungsten hydrides WH(CO)$_{2}$(NO)L$

Content Provider	SpringerLink
Author	Belkova, N. V. Epstein, L. M. Krylova, A. I. Faerstein, E. G. Shubina, E. S.
Copyright Year	2007
Abstract	The kinetics of protonation of tungsten hydrides WH(CO)$_{2}$(NO)L$_{2}$ (1, L = PMe$_{3}$, PEt$_{3}$, P(OPri)$_{3}$, PPh$_{3}$) by weak OH-acids (PhOH, (CF$_{3}$)$_{2}$CHOH, (CF$_{3}$)$_{3}$COH) in hexane was studied by IR spectroscopy. The study of the reactions of compounds 1 with OH-acids at 190–270 K revealed that the first step involves the formation of dihydrogen-bonded W(CO)$_{2}$(NO)L$_{2}$(H)...HOR complexes. When the temperature increases to ambient, the proton transfer and evolution of molecular hydrogen occur, affording the final products: organyloxy derivatives W(OR)(CO)$_{2}$(NO)L$_{2}$. The study of the kinetics at 298 K found that the proton transfer is the rate-determining step. The rate constants k $_{app}$ are 2.2·10$^{−5}$–6.3·10$^{−4}$ s$^{−1}$, and the free activation energies are ΔG $^{≠}$ $_{298K}$ = 22–23 kcal mol$^{−1}$. The rate constants depend on the proton-accepting properties of the hydride and the acidic properties of the OH-proton donor and increase in the same order as the enthalpy of hydrogen bond formation.
Starting Page	870
Ending Page	874
Page Count	5
File Format	PDF
ISSN	10665285
Journal	Russian Chemical Bulletin
Volume Number	56
Issue Number	5
e-ISSN	15739171
Language	English
Publisher	Springer US
Publisher Date	2007-01-01
Publisher Place	Boston
Access Restriction	Subscribed
Subject Keyword	tungsten hydrides dihydrogen bonds proton transfer kinetics IR spectroscopy Chemistry/Food Science Organic Chemistry Inorganic Chemistry
Content Type	Text
Resource Type	Article
Subject	Chemistry

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