Isotope effects on hydride transfer reactions from transition metal hydrides to trityl cation. An inverse isotope effect for a hydride transfer

Tan Yun Cheng, R Morris Bullock

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Abstract

Hydride transfer from transition metal hydrides (MH) to Ph3C+BF4 - gives M-FBF3 and Ph3CH. Deuterium kinetic isotope effects were determined for several MH/MD pairs (CH2Cl2 solution, 25°C). For hydride transfer from Cp(*)(CO)3MoH (Cp(*) = η5-C5Me5) to substituted trityl cations containing zero, one, two, or three p-MeO groups [Ph(n)(p-MeOC6H4)3- (n)C+BF4 -; n = 3, 2, 1, 0], the isotope effect remains essentially constant at k(MoH)/k(MoD) = 1.7-1.9 as the rate constant decreases from k(H) = 6.5 x 103 to 1.4 M-1 s-1. For hydride transfer to Ph3C+BF4 - from five metal hydrides [Cp(CO)3MoH, Cp(*)(CO)3WH, (indenyl)(CO)3WH, Cp(*)(CO)3MoH, and trans-Cp(CO)2(PCy3)MoH; Cp = η5-C5H5] with second- order rate constants k(H)- ≥ 3.8 x 102 M-1 s-1, the kinetic isotope effects are also k(MH)/k(MD) = 1.7-1.8. For a series of five tungsten hydrides with substituted Cp ligands, the kinetic isotope effects decrease from k(WH)k(WD) = 1.8 to 0.47 as the rate constant decreases (from k(H)- = 2.0 x 103 to 0.72 M-1 s-1). The steadily decreasing values of k(MH)/k(MD) with decreasing rate constants of hydride transfer are interpreted as indicating progressively stronger force constants of isotopically sensitive modes of the transition state, as the reaction slows clown in progressing from more electron-donating Cp ligands to less electron- rich Cp ligands. The inverse isotope effect (k(WH)/k(WD) = 0.47) found for the slowest tungsten hydride, (C5H4CO2Me)(CO)3WH, is proposed to be due to a product-like transition state for irreversible hydride transfer.

Original languageEnglish
Pages (from-to)3150-3155
Number of pages6
JournalJournal of the American Chemical Society
Volume121
Issue number13
DOIs
Publication statusPublished - Apr 7 1999

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Hydrides
Isotopes
Transition metals
Cations
Positive ions
Metals
Tungsten
Ligands
Electrons
Rate constants
Deuterium
Kinetics

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

@article{60ed810b806543ba920e24e391a2eec0,
title = "Isotope effects on hydride transfer reactions from transition metal hydrides to trityl cation. An inverse isotope effect for a hydride transfer",
abstract = "Hydride transfer from transition metal hydrides (MH) to Ph3C+BF4 - gives M-FBF3 and Ph3CH. Deuterium kinetic isotope effects were determined for several MH/MD pairs (CH2Cl2 solution, 25°C). For hydride transfer from Cp(*)(CO)3MoH (Cp(*) = η5-C5Me5) to substituted trityl cations containing zero, one, two, or three p-MeO groups [Ph(n)(p-MeOC6H4)3- (n)C+BF4 -; n = 3, 2, 1, 0], the isotope effect remains essentially constant at k(MoH)/k(MoD) = 1.7-1.9 as the rate constant decreases from k(H) = 6.5 x 103 to 1.4 M-1 s-1. For hydride transfer to Ph3C+BF4 - from five metal hydrides [Cp(CO)3MoH, Cp(*)(CO)3WH, (indenyl)(CO)3WH, Cp(*)(CO)3MoH, and trans-Cp(CO)2(PCy3)MoH; Cp = η5-C5H5] with second- order rate constants k(H)- ≥ 3.8 x 102 M-1 s-1, the kinetic isotope effects are also k(MH)/k(MD) = 1.7-1.8. For a series of five tungsten hydrides with substituted Cp ligands, the kinetic isotope effects decrease from k(WH)k(WD) = 1.8 to 0.47 as the rate constant decreases (from k(H)- = 2.0 x 103 to 0.72 M-1 s-1). The steadily decreasing values of k(MH)/k(MD) with decreasing rate constants of hydride transfer are interpreted as indicating progressively stronger force constants of isotopically sensitive modes of the transition state, as the reaction slows clown in progressing from more electron-donating Cp ligands to less electron- rich Cp ligands. The inverse isotope effect (k(WH)/k(WD) = 0.47) found for the slowest tungsten hydride, (C5H4CO2Me)(CO)3WH, is proposed to be due to a product-like transition state for irreversible hydride transfer.",
author = "Cheng, {Tan Yun} and Bullock, {R Morris}",
year = "1999",
month = "4",
day = "7",
doi = "10.1021/ja983448x",
language = "English",
volume = "121",
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journal = "Journal of the American Chemical Society",
issn = "0002-7863",
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T1 - Isotope effects on hydride transfer reactions from transition metal hydrides to trityl cation. An inverse isotope effect for a hydride transfer

AU - Cheng, Tan Yun

AU - Bullock, R Morris

PY - 1999/4/7

Y1 - 1999/4/7

N2 - Hydride transfer from transition metal hydrides (MH) to Ph3C+BF4 - gives M-FBF3 and Ph3CH. Deuterium kinetic isotope effects were determined for several MH/MD pairs (CH2Cl2 solution, 25°C). For hydride transfer from Cp(*)(CO)3MoH (Cp(*) = η5-C5Me5) to substituted trityl cations containing zero, one, two, or three p-MeO groups [Ph(n)(p-MeOC6H4)3- (n)C+BF4 -; n = 3, 2, 1, 0], the isotope effect remains essentially constant at k(MoH)/k(MoD) = 1.7-1.9 as the rate constant decreases from k(H) = 6.5 x 103 to 1.4 M-1 s-1. For hydride transfer to Ph3C+BF4 - from five metal hydrides [Cp(CO)3MoH, Cp(*)(CO)3WH, (indenyl)(CO)3WH, Cp(*)(CO)3MoH, and trans-Cp(CO)2(PCy3)MoH; Cp = η5-C5H5] with second- order rate constants k(H)- ≥ 3.8 x 102 M-1 s-1, the kinetic isotope effects are also k(MH)/k(MD) = 1.7-1.8. For a series of five tungsten hydrides with substituted Cp ligands, the kinetic isotope effects decrease from k(WH)k(WD) = 1.8 to 0.47 as the rate constant decreases (from k(H)- = 2.0 x 103 to 0.72 M-1 s-1). The steadily decreasing values of k(MH)/k(MD) with decreasing rate constants of hydride transfer are interpreted as indicating progressively stronger force constants of isotopically sensitive modes of the transition state, as the reaction slows clown in progressing from more electron-donating Cp ligands to less electron- rich Cp ligands. The inverse isotope effect (k(WH)/k(WD) = 0.47) found for the slowest tungsten hydride, (C5H4CO2Me)(CO)3WH, is proposed to be due to a product-like transition state for irreversible hydride transfer.

AB - Hydride transfer from transition metal hydrides (MH) to Ph3C+BF4 - gives M-FBF3 and Ph3CH. Deuterium kinetic isotope effects were determined for several MH/MD pairs (CH2Cl2 solution, 25°C). For hydride transfer from Cp(*)(CO)3MoH (Cp(*) = η5-C5Me5) to substituted trityl cations containing zero, one, two, or three p-MeO groups [Ph(n)(p-MeOC6H4)3- (n)C+BF4 -; n = 3, 2, 1, 0], the isotope effect remains essentially constant at k(MoH)/k(MoD) = 1.7-1.9 as the rate constant decreases from k(H) = 6.5 x 103 to 1.4 M-1 s-1. For hydride transfer to Ph3C+BF4 - from five metal hydrides [Cp(CO)3MoH, Cp(*)(CO)3WH, (indenyl)(CO)3WH, Cp(*)(CO)3MoH, and trans-Cp(CO)2(PCy3)MoH; Cp = η5-C5H5] with second- order rate constants k(H)- ≥ 3.8 x 102 M-1 s-1, the kinetic isotope effects are also k(MH)/k(MD) = 1.7-1.8. For a series of five tungsten hydrides with substituted Cp ligands, the kinetic isotope effects decrease from k(WH)k(WD) = 1.8 to 0.47 as the rate constant decreases (from k(H)- = 2.0 x 103 to 0.72 M-1 s-1). The steadily decreasing values of k(MH)/k(MD) with decreasing rate constants of hydride transfer are interpreted as indicating progressively stronger force constants of isotopically sensitive modes of the transition state, as the reaction slows clown in progressing from more electron-donating Cp ligands to less electron- rich Cp ligands. The inverse isotope effect (k(WH)/k(WD) = 0.47) found for the slowest tungsten hydride, (C5H4CO2Me)(CO)3WH, is proposed to be due to a product-like transition state for irreversible hydride transfer.

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