A simple entry to (η5-C5R5)chlorodioxomolybdenum(VI) complexes (R = H, CH3, CH2Ph) and their use as olefin epoxidation catalysts

Marta Abrantes, Ana M. Santos, J. Mink, Fritz E. Kühn, Carlos C. Romão

Research output: Contribution to journalArticle

146 Citations (Scopus)

Abstract

The complexes (η5-C5R5) MoO2Cl (R = H, CH3 (Me), CH2Ph (Bz)) are readily prepared from the parent carbonyls (η5-C5R5)Mo(CO)3Cl upon reaction with t-BuOOH (TBHP) in n-decane. The compounds are characterized by vibrational spectroscopy, 1H, 13C, and 95Mo NMR spectroscopy, and elementary analysis and are compared to their (η5-C5R5)ReO3 homologues. The Mo-C5R5 force constants have been determined. (η5-C5Bz5)MoO2Cl can be stored and handled at room temperature without decomposition, in contrast to the more temperature sensitive Cp (R = H) and Cp* (R = Me) analogues. The (η5-C5R5)MoO2Cl complexes catalyze the epoxidation of cyclooctene, styrene, and 1-octene with TBHP as oxidizing agent. The highest activity is found for (η5-C5Bz5)MoO2Cl: TOF 21000 mol/(mol × h) for cyclooctene in CH2Cl2 at 55°C with a ratio catalyst:substrate:TBHP = 0.0001:1:2.5. This activity even surpasses that of the well-known MeReO3/H2O2 system. The stable parent carbonyls (η5-C5R5)Mo(CO)3Cl can be used as catalyst precursors since they are transformed into (η5-C5R5)MoO2Cl under the operating catalytic conditions.

Original languageEnglish
Pages (from-to)2112-2118
Number of pages7
JournalOrganometallics
Volume22
Issue number10
DOIs
Publication statusPublished - May 12 2003

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epoxidation
Epoxidation
Alkenes
Carbon Monoxide
entry
alkenes
catalysts
Vibrational spectroscopy
Catalysts
Styrene
Oxidants
styrenes
spectroscopy
Nuclear magnetic resonance spectroscopy
analogs
Decomposition
decomposition
Temperature
nuclear magnetic resonance
room temperature

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

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A simple entry to (η5-C5R5)chlorodioxomolybdenum(VI) complexes (R = H, CH3, CH2Ph) and their use as olefin epoxidation catalysts. / Abrantes, Marta; Santos, Ana M.; Mink, J.; Kühn, Fritz E.; Romão, Carlos C.

In: Organometallics, Vol. 22, No. 10, 12.05.2003, p. 2112-2118.

Research output: Contribution to journalArticle

Abrantes, Marta ; Santos, Ana M. ; Mink, J. ; Kühn, Fritz E. ; Romão, Carlos C. / A simple entry to (η5-C5R5)chlorodioxomolybdenum(VI) complexes (R = H, CH3, CH2Ph) and their use as olefin epoxidation catalysts. In: Organometallics. 2003 ; Vol. 22, No. 10. pp. 2112-2118.
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abstract = "The complexes (η5-C5R5) MoO2Cl (R = H, CH3 (Me), CH2Ph (Bz)) are readily prepared from the parent carbonyls (η5-C5R5)Mo(CO)3Cl upon reaction with t-BuOOH (TBHP) in n-decane. The compounds are characterized by vibrational spectroscopy, 1H, 13C, and 95Mo NMR spectroscopy, and elementary analysis and are compared to their (η5-C5R5)ReO3 homologues. The Mo-C5R5 force constants have been determined. (η5-C5Bz5)MoO2Cl can be stored and handled at room temperature without decomposition, in contrast to the more temperature sensitive Cp (R = H) and Cp* (R = Me) analogues. The (η5-C5R5)MoO2Cl complexes catalyze the epoxidation of cyclooctene, styrene, and 1-octene with TBHP as oxidizing agent. The highest activity is found for (η5-C5Bz5)MoO2Cl: TOF 21000 mol/(mol × h) for cyclooctene in CH2Cl2 at 55°C with a ratio catalyst:substrate:TBHP = 0.0001:1:2.5. This activity even surpasses that of the well-known MeReO3/H2O2 system. The stable parent carbonyls (η5-C5R5)Mo(CO)3Cl can be used as catalyst precursors since they are transformed into (η5-C5R5)MoO2Cl under the operating catalytic conditions.",
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AB - The complexes (η5-C5R5) MoO2Cl (R = H, CH3 (Me), CH2Ph (Bz)) are readily prepared from the parent carbonyls (η5-C5R5)Mo(CO)3Cl upon reaction with t-BuOOH (TBHP) in n-decane. The compounds are characterized by vibrational spectroscopy, 1H, 13C, and 95Mo NMR spectroscopy, and elementary analysis and are compared to their (η5-C5R5)ReO3 homologues. The Mo-C5R5 force constants have been determined. (η5-C5Bz5)MoO2Cl can be stored and handled at room temperature without decomposition, in contrast to the more temperature sensitive Cp (R = H) and Cp* (R = Me) analogues. The (η5-C5R5)MoO2Cl complexes catalyze the epoxidation of cyclooctene, styrene, and 1-octene with TBHP as oxidizing agent. The highest activity is found for (η5-C5Bz5)MoO2Cl: TOF 21000 mol/(mol × h) for cyclooctene in CH2Cl2 at 55°C with a ratio catalyst:substrate:TBHP = 0.0001:1:2.5. This activity even surpasses that of the well-known MeReO3/H2O2 system. The stable parent carbonyls (η5-C5R5)Mo(CO)3Cl can be used as catalyst precursors since they are transformed into (η5-C5R5)MoO2Cl under the operating catalytic conditions.

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