Heats of reaction of (toluene)Mo(CO)3 with substituted arenes, sodium cyclopentadiene, nitriles, isocyanides, and other ligands. Solution thermodynamic study of ligand exchange in the complexes fac -L3Mo(CO)3

Steven P. Nolan, Ramon Lopez De La Vega, Carl Hoff

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Abstract

The results of solution calorimetric studies are used to measure the relative stability in solution of the following complexes: (arene)Mo(CO)3 (arene = o-xylene, m-xylene, p-xylene, N,N-dimethylaniline, p-bis(dimethylamino)benzene, (trimethylsilyl)benzene, sodium tetraphenylborate, and sodium cyclopentadiene), L3Mo(CO)3 (L = acetone, acetonitrile, benzonitrile, tert-butyl cyanide, tert-butyl isocyanide, cyclohexyl isocyanide, piperidine, and tributylphosphine oxide), and L*Mo(CO)3 (L* = bis(methoxyethyl) ether and potassium hydridotris(pyrazoyl) borate). The enthalpy of deprotonation of H-Mo(CO)3C5H5 by NaC5H5 has been measured and used to complete a thermochemical cycle comparing the heats of reaction of (toluene)Mo(CO)3 with C5H6 and NaC5H5. These results are combined with earlier data to yield enthalpies of ligand exchange: LnMo(CO)3 + n′L′ → L′n′Mo(CO)3 + nL which span over 50 kcal/mol and encompass a broad range of organometallic ligands. Factors involved in controlling Mo-L bond strengths are discussed.

Original languageEnglish
Pages (from-to)2529-2537
Number of pages9
JournalOrganometallics
Volume5
Issue number12
StatePublished - Dec 1 1986

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Cyclopentanes
Nitriles
nitriles
Toluene
Cyanides
xylene
Carbon Monoxide
toluene
Ion exchange
Sodium
sodium
Thermodynamics
Ligands
heat
thermodynamics
ligands
enthalpy
benzene
piperidine
cyanides

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

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title = "Heats of reaction of (toluene)Mo(CO)3 with substituted arenes, sodium cyclopentadiene, nitriles, isocyanides, and other ligands. Solution thermodynamic study of ligand exchange in the complexes fac -L3Mo(CO)3",
abstract = "The results of solution calorimetric studies are used to measure the relative stability in solution of the following complexes: (arene)Mo(CO)3 (arene = o-xylene, m-xylene, p-xylene, N,N-dimethylaniline, p-bis(dimethylamino)benzene, (trimethylsilyl)benzene, sodium tetraphenylborate, and sodium cyclopentadiene), L3Mo(CO)3 (L = acetone, acetonitrile, benzonitrile, tert-butyl cyanide, tert-butyl isocyanide, cyclohexyl isocyanide, piperidine, and tributylphosphine oxide), and L*Mo(CO)3 (L* = bis(methoxyethyl) ether and potassium hydridotris(pyrazoyl) borate). The enthalpy of deprotonation of H-Mo(CO)3C5H5 by NaC5H5 has been measured and used to complete a thermochemical cycle comparing the heats of reaction of (toluene)Mo(CO)3 with C5H6 and NaC5H5. These results are combined with earlier data to yield enthalpies of ligand exchange: LnMo(CO)3 + n′L′ → L′n′Mo(CO)3 + nL which span over 50 kcal/mol and encompass a broad range of organometallic ligands. Factors involved in controlling Mo-L bond strengths are discussed.",
author = "Nolan, {Steven P.} and {Lopez De La Vega}, Ramon and Carl Hoff",
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T1 - Heats of reaction of (toluene)Mo(CO)3 with substituted arenes, sodium cyclopentadiene, nitriles, isocyanides, and other ligands. Solution thermodynamic study of ligand exchange in the complexes fac -L3Mo(CO)3

AU - Nolan, Steven P.

AU - Lopez De La Vega, Ramon

AU - Hoff, Carl

PY - 1986/12/1

Y1 - 1986/12/1

N2 - The results of solution calorimetric studies are used to measure the relative stability in solution of the following complexes: (arene)Mo(CO)3 (arene = o-xylene, m-xylene, p-xylene, N,N-dimethylaniline, p-bis(dimethylamino)benzene, (trimethylsilyl)benzene, sodium tetraphenylborate, and sodium cyclopentadiene), L3Mo(CO)3 (L = acetone, acetonitrile, benzonitrile, tert-butyl cyanide, tert-butyl isocyanide, cyclohexyl isocyanide, piperidine, and tributylphosphine oxide), and L*Mo(CO)3 (L* = bis(methoxyethyl) ether and potassium hydridotris(pyrazoyl) borate). The enthalpy of deprotonation of H-Mo(CO)3C5H5 by NaC5H5 has been measured and used to complete a thermochemical cycle comparing the heats of reaction of (toluene)Mo(CO)3 with C5H6 and NaC5H5. These results are combined with earlier data to yield enthalpies of ligand exchange: LnMo(CO)3 + n′L′ → L′n′Mo(CO)3 + nL which span over 50 kcal/mol and encompass a broad range of organometallic ligands. Factors involved in controlling Mo-L bond strengths are discussed.

AB - The results of solution calorimetric studies are used to measure the relative stability in solution of the following complexes: (arene)Mo(CO)3 (arene = o-xylene, m-xylene, p-xylene, N,N-dimethylaniline, p-bis(dimethylamino)benzene, (trimethylsilyl)benzene, sodium tetraphenylborate, and sodium cyclopentadiene), L3Mo(CO)3 (L = acetone, acetonitrile, benzonitrile, tert-butyl cyanide, tert-butyl isocyanide, cyclohexyl isocyanide, piperidine, and tributylphosphine oxide), and L*Mo(CO)3 (L* = bis(methoxyethyl) ether and potassium hydridotris(pyrazoyl) borate). The enthalpy of deprotonation of H-Mo(CO)3C5H5 by NaC5H5 has been measured and used to complete a thermochemical cycle comparing the heats of reaction of (toluene)Mo(CO)3 with C5H6 and NaC5H5. These results are combined with earlier data to yield enthalpies of ligand exchange: LnMo(CO)3 + n′L′ → L′n′Mo(CO)3 + nL which span over 50 kcal/mol and encompass a broad range of organometallic ligands. Factors involved in controlling Mo-L bond strengths are discussed.

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