Reactions of the complexes M(Pr3)2(CO)3(M = Cr, Mo, W; R = iPr, Cy) with thiols, hydrogen sulfide, disulfides, hydrogen iodide and iodine. The role of heteroatoms in determining the metal-hydrogen bond strength at a sterically crowded metal center

Russel F. Lang; Telvin D. Ju; Gabor Kiss; Carl D. Hoff; Jeffrey C. Bryan; Gregory J. Kubas

doi:10.1016/s0020-1693(97)05510-2

Reactions of the complexes M(Pr₃)₂(CO)₃(M = Cr, Mo, W; R = ⁱPr, Cy) with thiols, hydrogen sulfide, disulfides, hydrogen iodide and iodine. The role of heteroatoms in determining the metal-hydrogen bond strength at a sterically crowded metal center

Russel F. Lang, Telvin D. Ju, Gabor Kiss, Carl D. Hoff, Jeffrey C. Bryan, Gregory J. Kubas

Chemistry

Research output: Contribution to journal › Article › peer-review

19 Scopus citations

Abstract

The complexes M(PCy₃)₂(CO)₃ (M = Cr, Mo, W) react with phenyl disulfide to form stable 17-electron radical complexes ^.M(PCy₃)₂(CO)₃(SPh). Reaction with other alkyl and aryl disulfides also yields stable radicals and reaction with I₂ yields ^.W(PⁱPr₃)₂(CO)₃(I). Reaction with thiols, hydrogen sulfide and hydrogen iodide yield the corresponding 18-electron hydrides W(PⁱPr₃)₂(CO)₃(H)(X). The crystal structure of W(PⁱPr₃)₂(CO)₃(H)(I) is reported and allows comparison with the structure of the radical complex ^.W(PⁱPr₃)₂(CO)₃(I). The W-H bond strengths in these heteroatom complexes are low, 55-57 kcal mol^-1. In spite of steric crowding, H atom transfer from W(PⁱPr₃)₂(CO)₃(H)(SPh) to ^.Cr(CO)₂(PPh₃)Cp occurs readily due to the stronger nature of the Cr-H bond formed. The chromium radical does not appear to attack the molecular hydrogen complex W(Pr₃)₂(CO)₃(H₂) or its dihydride form W(Pr₃)₂(CO)₃(H)₂ based on rate of hydrogenation studies. Phenyl disulfide does react with either W(Pr₃)₂(CO)₃(H₂) or its dihydride tautomer W(Pr₃)₂(CO)₃(H)₂ to form thiophenol and W(Pr₃)₂(CO)₃(SPh^.). This reaction is proposed to proceed by reaction of ^.SPh radicals which are generated in situ. These studies are used to bracket the first W-H bond dissociation energy in W(Pr₃)₂(CO)₃(H)₂. Additional studies of H atom and heteoratom transfer are described.

Original language	English (US)
Pages (from-to)	317-327
Number of pages	11
Journal	Inorganica Chimica Acta
Volume	259
Issue number	1-2
DOIs	https://doi.org/10.1016/s0020-1693(97)05510-2
State	Published - Jun 1997

Keywords

Chromium complexes
Hydrogen sulfide complexes
Molybdenum complexes
Thiol complexes
Tungsten complexes

ASJC Scopus subject areas

Biochemistry
Inorganic Chemistry
Physical and Theoretical Chemistry
Materials Chemistry

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Lang, R. F., Ju, T. D., Kiss, G., Hoff, C. D., Bryan, J. C., & Kubas, G. J. (1997). Reactions of the complexes M(Pr₃)₂(CO)₃(M = Cr, Mo, W; R = ⁱPr, Cy) with thiols, hydrogen sulfide, disulfides, hydrogen iodide and iodine. The role of heteroatoms in determining the metal-hydrogen bond strength at a sterically crowded metal center. Inorganica Chimica Acta, 259(1-2), 317-327. https://doi.org/10.1016/s0020-1693(97)05510-2

Reactions of the complexes M(Pr₃)₂(CO)₃(M = Cr, Mo, W; R = ⁱPr, Cy) with thiols, hydrogen sulfide, disulfides, hydrogen iodide and iodine. The role of heteroatoms in determining the metal-hydrogen bond strength at a sterically crowded metal center. / Lang, Russel F.; Ju, Telvin D.; Kiss, Gabor; Hoff, Carl D.; Bryan, Jeffrey C.; Kubas, Gregory J.

In: Inorganica Chimica Acta, Vol. 259, No. 1-2, 06.1997, p. 317-327.

Research output: Contribution to journal › Article › peer-review

Lang, RF, Ju, TD, Kiss, G, Hoff, CD, Bryan, JC & Kubas, GJ 1997, 'Reactions of the complexes M(Pr₃)₂(CO)₃(M = Cr, Mo, W; R = ⁱPr, Cy) with thiols, hydrogen sulfide, disulfides, hydrogen iodide and iodine. The role of heteroatoms in determining the metal-hydrogen bond strength at a sterically crowded metal center', Inorganica Chimica Acta, vol. 259, no. 1-2, pp. 317-327. https://doi.org/10.1016/s0020-1693(97)05510-2

Lang RF, Ju TD, Kiss G, Hoff CD, Bryan JC, Kubas GJ. Reactions of the complexes M(Pr₃)₂(CO)₃(M = Cr, Mo, W; R = ⁱPr, Cy) with thiols, hydrogen sulfide, disulfides, hydrogen iodide and iodine. The role of heteroatoms in determining the metal-hydrogen bond strength at a sterically crowded metal center. Inorganica Chimica Acta. 1997 Jun;259(1-2):317-327. https://doi.org/10.1016/s0020-1693(97)05510-2

Lang, Russel F. ; Ju, Telvin D. ; Kiss, Gabor ; Hoff, Carl D. ; Bryan, Jeffrey C. ; Kubas, Gregory J. / Reactions of the complexes M(Pr₃)₂(CO)₃(M = Cr, Mo, W; R = ⁱPr, Cy) with thiols, hydrogen sulfide, disulfides, hydrogen iodide and iodine. The role of heteroatoms in determining the metal-hydrogen bond strength at a sterically crowded metal center. In: Inorganica Chimica Acta. 1997 ; Vol. 259, No. 1-2. pp. 317-327.

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title = "Reactions of the complexes M(Pr3)2(CO)3(M = Cr, Mo, W; R = iPr, Cy) with thiols, hydrogen sulfide, disulfides, hydrogen iodide and iodine. The role of heteroatoms in determining the metal-hydrogen bond strength at a sterically crowded metal center",

abstract = "The complexes M(PCy3)2(CO)3 (M = Cr, Mo, W) react with phenyl disulfide to form stable 17-electron radical complexes .M(PCy3)2(CO)3(SPh). Reaction with other alkyl and aryl disulfides also yields stable radicals and reaction with I2 yields .W(PiPr3)2(CO)3(I). Reaction with thiols, hydrogen sulfide and hydrogen iodide yield the corresponding 18-electron hydrides W(PiPr3)2(CO)3(H)(X). The crystal structure of W(PiPr3)2(CO)3(H)(I) is reported and allows comparison with the structure of the radical complex .W(PiPr3)2(CO)3(I). The W-H bond strengths in these heteroatom complexes are low, 55-57 kcal mol-1. In spite of steric crowding, H atom transfer from W(PiPr3)2(CO)3(H)(SPh) to .Cr(CO)2(PPh3)Cp occurs readily due to the stronger nature of the Cr-H bond formed. The chromium radical does not appear to attack the molecular hydrogen complex W(Pr3)2(CO)3(H2) or its dihydride form W(Pr3)2(CO)3(H)2 based on rate of hydrogenation studies. Phenyl disulfide does react with either W(Pr3)2(CO)3(H2) or its dihydride tautomer W(Pr3)2(CO)3(H)2 to form thiophenol and W(Pr3)2(CO)3(SPh.). This reaction is proposed to proceed by reaction of .SPh radicals which are generated in situ. These studies are used to bracket the first W-H bond dissociation energy in W(Pr3)2(CO)3(H)2. Additional studies of H atom and heteoratom transfer are described.",

keywords = "Chromium complexes, Hydrogen sulfide complexes, Molybdenum complexes, Thiol complexes, Tungsten complexes",

author = "Lang, {Russel F.} and Ju, {Telvin D.} and Gabor Kiss and Hoff, {Carl D.} and Bryan, {Jeffrey C.} and Kubas, {Gregory J.}",

note = "Funding Information: Support of this work by the National Science Foundation grantCHE-9221265 (C.D.H.) andtheDepartmentofEnergy (G.J.K.) is gratefully acknowledged. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.",

year = "1997",

month = jun,

doi = "10.1016/s0020-1693(97)05510-2",

language = "English (US)",

volume = "259",

pages = "317--327",

journal = "Inorganica Chimica Acta",

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T1 - Reactions of the complexes M(Pr3)2(CO)3(M = Cr, Mo, W; R = iPr, Cy) with thiols, hydrogen sulfide, disulfides, hydrogen iodide and iodine. The role of heteroatoms in determining the metal-hydrogen bond strength at a sterically crowded metal center

AU - Lang, Russel F.

AU - Ju, Telvin D.

AU - Kiss, Gabor

AU - Hoff, Carl D.

AU - Bryan, Jeffrey C.

AU - Kubas, Gregory J.

N1 - Funding Information: Support of this work by the National Science Foundation grantCHE-9221265 (C.D.H.) andtheDepartmentofEnergy (G.J.K.) is gratefully acknowledged. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 1997/6

Y1 - 1997/6

N2 - The complexes M(PCy3)2(CO)3 (M = Cr, Mo, W) react with phenyl disulfide to form stable 17-electron radical complexes .M(PCy3)2(CO)3(SPh). Reaction with other alkyl and aryl disulfides also yields stable radicals and reaction with I2 yields .W(PiPr3)2(CO)3(I). Reaction with thiols, hydrogen sulfide and hydrogen iodide yield the corresponding 18-electron hydrides W(PiPr3)2(CO)3(H)(X). The crystal structure of W(PiPr3)2(CO)3(H)(I) is reported and allows comparison with the structure of the radical complex .W(PiPr3)2(CO)3(I). The W-H bond strengths in these heteroatom complexes are low, 55-57 kcal mol-1. In spite of steric crowding, H atom transfer from W(PiPr3)2(CO)3(H)(SPh) to .Cr(CO)2(PPh3)Cp occurs readily due to the stronger nature of the Cr-H bond formed. The chromium radical does not appear to attack the molecular hydrogen complex W(Pr3)2(CO)3(H2) or its dihydride form W(Pr3)2(CO)3(H)2 based on rate of hydrogenation studies. Phenyl disulfide does react with either W(Pr3)2(CO)3(H2) or its dihydride tautomer W(Pr3)2(CO)3(H)2 to form thiophenol and W(Pr3)2(CO)3(SPh.). This reaction is proposed to proceed by reaction of .SPh radicals which are generated in situ. These studies are used to bracket the first W-H bond dissociation energy in W(Pr3)2(CO)3(H)2. Additional studies of H atom and heteoratom transfer are described.

AB - The complexes M(PCy3)2(CO)3 (M = Cr, Mo, W) react with phenyl disulfide to form stable 17-electron radical complexes .M(PCy3)2(CO)3(SPh). Reaction with other alkyl and aryl disulfides also yields stable radicals and reaction with I2 yields .W(PiPr3)2(CO)3(I). Reaction with thiols, hydrogen sulfide and hydrogen iodide yield the corresponding 18-electron hydrides W(PiPr3)2(CO)3(H)(X). The crystal structure of W(PiPr3)2(CO)3(H)(I) is reported and allows comparison with the structure of the radical complex .W(PiPr3)2(CO)3(I). The W-H bond strengths in these heteroatom complexes are low, 55-57 kcal mol-1. In spite of steric crowding, H atom transfer from W(PiPr3)2(CO)3(H)(SPh) to .Cr(CO)2(PPh3)Cp occurs readily due to the stronger nature of the Cr-H bond formed. The chromium radical does not appear to attack the molecular hydrogen complex W(Pr3)2(CO)3(H2) or its dihydride form W(Pr3)2(CO)3(H)2 based on rate of hydrogenation studies. Phenyl disulfide does react with either W(Pr3)2(CO)3(H2) or its dihydride tautomer W(Pr3)2(CO)3(H)2 to form thiophenol and W(Pr3)2(CO)3(SPh.). This reaction is proposed to proceed by reaction of .SPh radicals which are generated in situ. These studies are used to bracket the first W-H bond dissociation energy in W(Pr3)2(CO)3(H)2. Additional studies of H atom and heteoratom transfer are described.

KW - Chromium complexes

KW - Hydrogen sulfide complexes

KW - Molybdenum complexes

KW - Thiol complexes

KW - Tungsten complexes

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