Synthesis and structure of CpMo(CO)(dppe)H and its oxidation by Ph 3C +

Tan Yun Cheng, David J. Szalda, Jie Zhang, R Morris Bullock

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

The reaction of CpMo(CO)(dppe)Cl (dppe = Ph 2PCH 2CH 2PPh 2) with Na +[AlH 2(OCH 2CH 2OCH 3) 2] - gives the molybdenum hydride complex CpMo(CO)(dppe)H, the structure of which was determined by X-ray crystallography. Electrochemical oxidation of CpMo(CO)(dppe)H in CH 3CN is quasi-reversible, with the peak potential at -0.15 V (vs Fc/Fc +). The reaction of CpMo(CO)(dppe)H with 1 equiv of Ph 3C +BF 4 - in CD 3CN gives [CpMo(CO)(dppe)-(NCCD 3)] + as the organometallic product, along with dihydrogen and Gomberg's dimer (which is formed by dimerization of Ph 3C ). The proposed mechanism involves one-electron oxidation of CpMo(CO)(dppe)H by Ph 3C + to give the radical-cation complex [CpMo(CO)(dppe)H] •+. Proton transfer from [CpMo(CO)(dppe)H] •+ to CpMo(CO)(dppe)H, loss of dihydrogen from [CpMo(CO)(dppe)(H) 2] +, and oxidation of Cp(CO)(dppe)Mo by Ph 3C + lead to the observed products. In the presence of an amine base, the stoichiometry changes, with 2 equiv of Ph 3C + being required for each 1 equiv of CpMo(CO)(dppe)H because of deprotonation of [CpMo(CO)(dppe)H] •+ by the amine. Protonation of CpMo(CO)(dppe)H by HOTf provides the dihydride complex [CpMo(CO)(dppe)(H) 2] +OTf -, which loses dihydrogen to generate CpMo(CO)(dppe)(OTf).

Original languageEnglish
Pages (from-to)4712-4720
Number of pages9
JournalInorganic Chemistry
Volume45
Issue number12
DOIs
Publication statusPublished - Jun 12 2006

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Oxidation
Hydrogen
oxidation
Amines
synthesis
Deprotonation
Proton transfer
Molybdenum
Dimerization
Electrochemical oxidation
Protonation
X ray crystallography
Organometallics
Hydrides
Stoichiometry
Dimers
Cations
amines
dihydrides
electrochemical oxidation

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Synthesis and structure of CpMo(CO)(dppe)H and its oxidation by Ph 3C + . / Cheng, Tan Yun; Szalda, David J.; Zhang, Jie; Bullock, R Morris.

In: Inorganic Chemistry, Vol. 45, No. 12, 12.06.2006, p. 4712-4720.

Research output: Contribution to journalArticle

Cheng, Tan Yun ; Szalda, David J. ; Zhang, Jie ; Bullock, R Morris. / Synthesis and structure of CpMo(CO)(dppe)H and its oxidation by Ph 3C + . In: Inorganic Chemistry. 2006 ; Vol. 45, No. 12. pp. 4712-4720.
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title = "Synthesis and structure of CpMo(CO)(dppe)H and its oxidation by Ph 3C +",
abstract = "The reaction of CpMo(CO)(dppe)Cl (dppe = Ph 2PCH 2CH 2PPh 2) with Na +[AlH 2(OCH 2CH 2OCH 3) 2] - gives the molybdenum hydride complex CpMo(CO)(dppe)H, the structure of which was determined by X-ray crystallography. Electrochemical oxidation of CpMo(CO)(dppe)H in CH 3CN is quasi-reversible, with the peak potential at -0.15 V (vs Fc/Fc +). The reaction of CpMo(CO)(dppe)H with 1 equiv of Ph 3C +BF 4 - in CD 3CN gives [CpMo(CO)(dppe)-(NCCD 3)] + as the organometallic product, along with dihydrogen and Gomberg's dimer (which is formed by dimerization of Ph 3C •). The proposed mechanism involves one-electron oxidation of CpMo(CO)(dppe)H by Ph 3C + to give the radical-cation complex [CpMo(CO)(dppe)H] •+. Proton transfer from [CpMo(CO)(dppe)H] •+ to CpMo(CO)(dppe)H, loss of dihydrogen from [CpMo(CO)(dppe)(H) 2] +, and oxidation of Cp(CO)(dppe)Mo • by Ph 3C + lead to the observed products. In the presence of an amine base, the stoichiometry changes, with 2 equiv of Ph 3C + being required for each 1 equiv of CpMo(CO)(dppe)H because of deprotonation of [CpMo(CO)(dppe)H] •+ by the amine. Protonation of CpMo(CO)(dppe)H by HOTf provides the dihydride complex [CpMo(CO)(dppe)(H) 2] +OTf -, which loses dihydrogen to generate CpMo(CO)(dppe)(OTf).",
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T1 - Synthesis and structure of CpMo(CO)(dppe)H and its oxidation by Ph 3C +

AU - Cheng, Tan Yun

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N2 - The reaction of CpMo(CO)(dppe)Cl (dppe = Ph 2PCH 2CH 2PPh 2) with Na +[AlH 2(OCH 2CH 2OCH 3) 2] - gives the molybdenum hydride complex CpMo(CO)(dppe)H, the structure of which was determined by X-ray crystallography. Electrochemical oxidation of CpMo(CO)(dppe)H in CH 3CN is quasi-reversible, with the peak potential at -0.15 V (vs Fc/Fc +). The reaction of CpMo(CO)(dppe)H with 1 equiv of Ph 3C +BF 4 - in CD 3CN gives [CpMo(CO)(dppe)-(NCCD 3)] + as the organometallic product, along with dihydrogen and Gomberg's dimer (which is formed by dimerization of Ph 3C •). The proposed mechanism involves one-electron oxidation of CpMo(CO)(dppe)H by Ph 3C + to give the radical-cation complex [CpMo(CO)(dppe)H] •+. Proton transfer from [CpMo(CO)(dppe)H] •+ to CpMo(CO)(dppe)H, loss of dihydrogen from [CpMo(CO)(dppe)(H) 2] +, and oxidation of Cp(CO)(dppe)Mo • by Ph 3C + lead to the observed products. In the presence of an amine base, the stoichiometry changes, with 2 equiv of Ph 3C + being required for each 1 equiv of CpMo(CO)(dppe)H because of deprotonation of [CpMo(CO)(dppe)H] •+ by the amine. Protonation of CpMo(CO)(dppe)H by HOTf provides the dihydride complex [CpMo(CO)(dppe)(H) 2] +OTf -, which loses dihydrogen to generate CpMo(CO)(dppe)(OTf).

AB - The reaction of CpMo(CO)(dppe)Cl (dppe = Ph 2PCH 2CH 2PPh 2) with Na +[AlH 2(OCH 2CH 2OCH 3) 2] - gives the molybdenum hydride complex CpMo(CO)(dppe)H, the structure of which was determined by X-ray crystallography. Electrochemical oxidation of CpMo(CO)(dppe)H in CH 3CN is quasi-reversible, with the peak potential at -0.15 V (vs Fc/Fc +). The reaction of CpMo(CO)(dppe)H with 1 equiv of Ph 3C +BF 4 - in CD 3CN gives [CpMo(CO)(dppe)-(NCCD 3)] + as the organometallic product, along with dihydrogen and Gomberg's dimer (which is formed by dimerization of Ph 3C •). The proposed mechanism involves one-electron oxidation of CpMo(CO)(dppe)H by Ph 3C + to give the radical-cation complex [CpMo(CO)(dppe)H] •+. Proton transfer from [CpMo(CO)(dppe)H] •+ to CpMo(CO)(dppe)H, loss of dihydrogen from [CpMo(CO)(dppe)(H) 2] +, and oxidation of Cp(CO)(dppe)Mo • by Ph 3C + lead to the observed products. In the presence of an amine base, the stoichiometry changes, with 2 equiv of Ph 3C + being required for each 1 equiv of CpMo(CO)(dppe)H because of deprotonation of [CpMo(CO)(dppe)H] •+ by the amine. Protonation of CpMo(CO)(dppe)H by HOTf provides the dihydride complex [CpMo(CO)(dppe)(H) 2] +OTf -, which loses dihydrogen to generate CpMo(CO)(dppe)(OTf).

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