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Title: Kinetic and thermodynamic acidity of hydrido transition-metal complexes. 3. Thermodynamic acidity of common mononuclear carbonyl hydrides

Abstract

The pK/sub a/ values of the common mononuclear carbonyl hydrides have been determined in acetonitrile by IR measurement of the position of deprotonation equilibria with various nitrogen bases and potassium phenolate. The resulting values cover a range of about 20 pK/sub a/ units, from 8.3 for HCo(CO)/sub 4/ to 26.6 for CpW(CO)/sub 2/(PMe/sub 3/)H. Hydrides with eta/sup 5/-C/sub 5/Me/sub 5/ ligands are appreciably weaker acids than the corresponding hydrides with eta/sup 5/-C/sub 5/H/sub 5/ ligands (e.g., the pK/sub a/ of (eta/sup 5/-C/sub 5/Me/sub 5/)Fe(CO)/sub 2/H is 26.3, while that of (eta/sup 5/-C/sub 5/H/sub 5/)Fe(CO)/sub 2/H is 19.4). The acidities of the group 8 carbonyl hydrides H/sub 2/M(CO)/sub 4/ decrease in the order Fe > Ru > Os.

Authors:
; ;
Publication Date:
Research Org.:
Colorado State Univ., Fort Collins
OSTI Identifier:
5659050
Resource Type:
Journal Article
Resource Relation:
Journal Name: J. Am. Chem. Soc.; (United States); Journal Volume: 108:9
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CARBONYLS; CHEMICAL REACTION KINETICS; THERMODYNAMIC ACTIVITY; HYDRIDES; METALS; ACETONITRILE; EQUILIBRIUM; EXPERIMENTAL DATA; LIGANDS; PH VALUE; THERMODYNAMICS; DATA; ELEMENTS; HYDROGEN COMPOUNDS; INFORMATION; KINETICS; NITRILES; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; REACTION KINETICS; 400201* - Chemical & Physicochemical Properties; 400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)

Citation Formats

Moore, E.J., Sullivan, J.M., and Norton, J.R. Kinetic and thermodynamic acidity of hydrido transition-metal complexes. 3. Thermodynamic acidity of common mononuclear carbonyl hydrides. United States: N. p., 1986. Web. doi:10.1021/ja00269a022.
Moore, E.J., Sullivan, J.M., & Norton, J.R. Kinetic and thermodynamic acidity of hydrido transition-metal complexes. 3. Thermodynamic acidity of common mononuclear carbonyl hydrides. United States. doi:10.1021/ja00269a022.
Moore, E.J., Sullivan, J.M., and Norton, J.R. Wed . "Kinetic and thermodynamic acidity of hydrido transition-metal complexes. 3. Thermodynamic acidity of common mononuclear carbonyl hydrides". United States. doi:10.1021/ja00269a022.
@article{osti_5659050,
title = {Kinetic and thermodynamic acidity of hydrido transition-metal complexes. 3. Thermodynamic acidity of common mononuclear carbonyl hydrides},
author = {Moore, E.J. and Sullivan, J.M. and Norton, J.R.},
abstractNote = {The pK/sub a/ values of the common mononuclear carbonyl hydrides have been determined in acetonitrile by IR measurement of the position of deprotonation equilibria with various nitrogen bases and potassium phenolate. The resulting values cover a range of about 20 pK/sub a/ units, from 8.3 for HCo(CO)/sub 4/ to 26.6 for CpW(CO)/sub 2/(PMe/sub 3/)H. Hydrides with eta/sup 5/-C/sub 5/Me/sub 5/ ligands are appreciably weaker acids than the corresponding hydrides with eta/sup 5/-C/sub 5/H/sub 5/ ligands (e.g., the pK/sub a/ of (eta/sup 5/-C/sub 5/Me/sub 5/)Fe(CO)/sub 2/H is 26.3, while that of (eta/sup 5/-C/sub 5/H/sub 5/)Fe(CO)/sub 2/H is 19.4). The acidities of the group 8 carbonyl hydrides H/sub 2/M(CO)/sub 4/ decrease in the order Fe > Ru > Os.},
doi = {10.1021/ja00269a022},
journal = {J. Am. Chem. Soc.; (United States)},
number = ,
volume = 108:9,
place = {United States},
year = {Wed Apr 30 00:00:00 EDT 1986},
month = {Wed Apr 30 00:00:00 EDT 1986}
}