Solution calorimetric, equilibrium, and synthetic studies of oxidative addition/reductive elimination of C5R5H (R = H, Me, indenyl) to/from the complexes M(CO)3(RCN)3/(η5-C5R 5)M(CO)3H (M = Cr, Mo, W)

Gregory J. Kubas, Gabor Kiss, Carl Hoff

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Abstract

Equilibrium data are reported for the reaction CpMo(CO)3H + 3MeCN ⇋ Mo(CO)3(MeCN)3 + CpH. Over the temperature range 43-82°C, ΔH = -11.2 kcal/mol, ΔS = -51.3 cal/(mol°C). Calorimetric data for the enthalpies of displacement of C5R5H by nitriles are reported: Cr, R = Me, -0.7 ± 0.7 kcal/mol, M = W, R = H, -5.6 ± 0.7, R = Me, -5.4 ± 0.7 kcal/mol. The enthalpy of reaction of Na+(indenyl)- with (p-xylene)Mo(CO)3 forming Na+Mo(CO)3(indenyl)- is -17.3 ± 0.2 kcal/mol, approximately 10 kcal/mol less than the corresponding reaction of Na+C5H5-. The heat of reaction of (indenyl) W(CO)3H with EtCN forming W(CO)3(EtCN)3, -20.0 ± 0.8 kcal/mol, is approximately 14 kcal/mol more exothermic than the corresponding reaction of the cyclopentadienyl complex, also in keeping with a reduced M-indenyl ground-state bond energy. Synthetic strategies to the (C5R5)M(CO)3H complexes are summarized.

Original languageEnglish
Pages (from-to)2870-2876
Number of pages7
JournalOrganometallics
Volume10
Issue number8
StatePublished - Dec 1 1991

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elimination
Enthalpy
Nitriles
Ground state
enthalpy
nitriles
xylene
Temperature
heat
ground state
Hot Temperature
4-xylene
temperature
energy

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

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title = "Solution calorimetric, equilibrium, and synthetic studies of oxidative addition/reductive elimination of C5R5H (R = H, Me, indenyl) to/from the complexes M(CO)3(RCN)3/(η5-C5R 5)M(CO)3H (M = Cr, Mo, W)",
abstract = "Equilibrium data are reported for the reaction CpMo(CO)3H + 3MeCN ⇋ Mo(CO)3(MeCN)3 + CpH. Over the temperature range 43-82°C, ΔH = -11.2 kcal/mol, ΔS = -51.3 cal/(mol°C). Calorimetric data for the enthalpies of displacement of C5R5H by nitriles are reported: Cr, R = Me, -0.7 ± 0.7 kcal/mol, M = W, R = H, -5.6 ± 0.7, R = Me, -5.4 ± 0.7 kcal/mol. The enthalpy of reaction of Na+(indenyl)- with (p-xylene)Mo(CO)3 forming Na+Mo(CO)3(indenyl)- is -17.3 ± 0.2 kcal/mol, approximately 10 kcal/mol less than the corresponding reaction of Na+C5H5-. The heat of reaction of (indenyl) W(CO)3H with EtCN forming W(CO)3(EtCN)3, -20.0 ± 0.8 kcal/mol, is approximately 14 kcal/mol more exothermic than the corresponding reaction of the cyclopentadienyl complex, also in keeping with a reduced M-indenyl ground-state bond energy. Synthetic strategies to the (C5R5)M(CO)3H complexes are summarized.",
author = "Kubas, {Gregory J.} and Gabor Kiss and Carl Hoff",
year = "1991",
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T1 - Solution calorimetric, equilibrium, and synthetic studies of oxidative addition/reductive elimination of C5R5H (R = H, Me, indenyl) to/from the complexes M(CO)3(RCN)3/(η5-C5R 5)M(CO)3H (M = Cr, Mo, W)

AU - Kubas, Gregory J.

AU - Kiss, Gabor

AU - Hoff, Carl

PY - 1991/12/1

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N2 - Equilibrium data are reported for the reaction CpMo(CO)3H + 3MeCN ⇋ Mo(CO)3(MeCN)3 + CpH. Over the temperature range 43-82°C, ΔH = -11.2 kcal/mol, ΔS = -51.3 cal/(mol°C). Calorimetric data for the enthalpies of displacement of C5R5H by nitriles are reported: Cr, R = Me, -0.7 ± 0.7 kcal/mol, M = W, R = H, -5.6 ± 0.7, R = Me, -5.4 ± 0.7 kcal/mol. The enthalpy of reaction of Na+(indenyl)- with (p-xylene)Mo(CO)3 forming Na+Mo(CO)3(indenyl)- is -17.3 ± 0.2 kcal/mol, approximately 10 kcal/mol less than the corresponding reaction of Na+C5H5-. The heat of reaction of (indenyl) W(CO)3H with EtCN forming W(CO)3(EtCN)3, -20.0 ± 0.8 kcal/mol, is approximately 14 kcal/mol more exothermic than the corresponding reaction of the cyclopentadienyl complex, also in keeping with a reduced M-indenyl ground-state bond energy. Synthetic strategies to the (C5R5)M(CO)3H complexes are summarized.

AB - Equilibrium data are reported for the reaction CpMo(CO)3H + 3MeCN ⇋ Mo(CO)3(MeCN)3 + CpH. Over the temperature range 43-82°C, ΔH = -11.2 kcal/mol, ΔS = -51.3 cal/(mol°C). Calorimetric data for the enthalpies of displacement of C5R5H by nitriles are reported: Cr, R = Me, -0.7 ± 0.7 kcal/mol, M = W, R = H, -5.6 ± 0.7, R = Me, -5.4 ± 0.7 kcal/mol. The enthalpy of reaction of Na+(indenyl)- with (p-xylene)Mo(CO)3 forming Na+Mo(CO)3(indenyl)- is -17.3 ± 0.2 kcal/mol, approximately 10 kcal/mol less than the corresponding reaction of Na+C5H5-. The heat of reaction of (indenyl) W(CO)3H with EtCN forming W(CO)3(EtCN)3, -20.0 ± 0.8 kcal/mol, is approximately 14 kcal/mol more exothermic than the corresponding reaction of the cyclopentadienyl complex, also in keeping with a reduced M-indenyl ground-state bond energy. Synthetic strategies to the (C5R5)M(CO)3H complexes are summarized.

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