Mechanistic Studies on the Roles of the Oxidant and Hydrogen Bonding in Determining the Selectivity in Alkene Oxidation in the Presence of Molybdenum Catalysts. Issue 6 (4th January 2013)

• Record Type: Journal Article
• Authors: Chandra, Prakash; Pandhare, Swati L.; Umbarkar, Shubhangi B.; Dongare, Mohan K.; Vanka, Kumar
• Is Part Of: Chemistry. Volume 19:Issue 6(2013)
• Page Start: 2030
• Page End: 2040
• Publication Date: 2013-01-04
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201202597
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>When the molybdenum oxo(peroxo) acetylide complex [CpMo(OO)(O)CCPh] is used as a catalyst for the oxidation of olefins, completely different product selectivity is obtained depending on the oxidant employed. When <italic>tert</italic>‐butyl hydroperoxide (TBHP, 5.5 <sc>M</sc>) in dodecane is used as the oxidant for the oxidation of cyclohexene, cyclohexene oxide is formed with high selectivity. However, when H₂O₂ is used as the oxidant, the corresponding <italic>cis</italic>‐1, 2‐diol is formed as the major product. Calculations performed by using density functional theory revealed the nature of the different competing mechanisms operating during the catalysis process and also provided an insight into the influence of the oxidant and hydrogen bonding on the catalysis process. The mechanistic investigations can therefore serve as a guide in the design of molybdenum‐based catalysts for the oxidation of olefins.</p> </abstract>