Please use this identifier to cite or link to this item: http://scholarbank.nus.edu.sg/handle/10635/94122
Title: Kinetic studies of the oxygen-atom transfer reactions between bis(diethyldithiocarbamato)dioxomolybdenum and triphenylphosphine
Authors: Huang, H.H. 
Huang, W. 
Yang, H.X.
Gao, P.L.
Han, D.G.
Keywords: Bis(diethyldithiocarbamato)dioxomolybdenum
Kinetics
Oxygen-atom transfer reaction
Reaction mechanism
Stopped-flow technique
Triphenylphosphine
Issue Date: 1997
Source: Huang, H.H.,Huang, W.,Yang, H.X.,Gao, P.L.,Han, D.G. (1997). Kinetic studies of the oxygen-atom transfer reactions between bis(diethyldithiocarbamato)dioxomolybdenum and triphenylphosphine. Polyhedron 16 (13) : 2163-2167. ScholarBank@NUS Repository.
Abstract: The kinetics of the oxygen-atom transfer reactions from bis(diethyldithiocarbamato)dioxomolybdenum [MoO2(S2CNEt2)2] to triphenylphosphine (PPh3) in several nonaqueous organic solvents were studied in detail by means of the stopped-flow technique at temperatures between 25 and 40°C. The kinetic and activation parameter data for the oxygen-atom transfer reactions in several nonaqueous solutions were obtained. It was found that the rate constants and the activation energies follow linear relationships vs the function of the refractive index (n2 - 1)/(2n2 + 1). In addition, it was also observed that the pre-exponential factor increases slightly with a decrease of (n2 - 1)/(2n2 + 1). Furthermore, two linear equations between the rate constant and the activation energy vs (n2 - 1)/(2n2 + 1) with good correlation coefficients were obtained. A one-step mechanism which supposes that the electrons of the lone pair on the P atom of triphenylphosphine enters directly into the π* antibonding orbital, which makes the Mo=O bond break, was proposed. © 1997 Elsevier Science Ltd. All rights reserved.
Source Title: Polyhedron
URI: http://scholarbank.nus.edu.sg/handle/10635/94122
ISSN: 02775387
Appears in Collections:Staff Publications

Show full item record
Files in This Item:
There are no files associated with this item.

Page view(s)

29
checked on Feb 17, 2018

Google ScholarTM

Check


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.