The Library
Palladium catalyzed oxidation of monoterpenes: NMR study of palladium(II)-monoterpene interactions
Tools
UNSPECIFIED (2005) Palladium catalyzed oxidation of monoterpenes: NMR study of palladium(II)-monoterpene interactions. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 690 (12). pp. 2996-3003. doi:10.1016/j.jorgancjem.2005.03.026 ISSN 0022-328X.
Research output not available from this repository.
Request-a-Copy directly from author or use local Library Get it For Me service.
Official URL: http://dx.doi.org/10.1016/j.jorgancjem.2005.03.026
Abstract
Reactions of the monoterpenes beta-pinene, limonene and myrcene with Pd(II) complexes in acetic acid solutions were studied by H-1 NMR spectroscopy. Various pi-allyl palladium complexes were detected in situ and their interaction with CuCl2 has been investigated. The results clarify the mechanism of allylic oxidation of these substrates mediated by Pd(II)/Cu(II)-based catalytic systems. Originally introduced to regenerate reduced palladium species, CuCl2 has been shown to play an important role in the formation and/or decomposition of key reaction intermediates - pi-allyl palladium complexes. P-Pinene and myrcene readily react with Pd(OAc)(2) giving corresponding pi-allyls, with two complexes acyclic and cyclic being formed from myrcene. On the other hand, the formation of pi-allyl complexes from limonene occurs at a significant rate only in the presence of CuCl2. NMR observations, including selective paramagnetic enhancement of spin-lattice relaxation, indicate that pi-allyl palladium intermediates specifically interact with Cu(II) ions in the reaction solutions. Such interaction probably involves Cu(II) bonding to Pd(II) via bridging ligands, and seems to be responsible for the accelerative effect of CuCl2 in the palladium catalyzed oxidation of the monoterpenes. Indeed, most of these reactions do not occur at all in the absence Of CuCl2. (c) 2005 Elsevier B.V. All rights reserved.
Item Type: | Journal Article | ||||
---|---|---|---|---|---|
Subjects: | Q Science > QD Chemistry | ||||
Journal or Publication Title: | JOURNAL OF ORGANOMETALLIC CHEMISTRY | ||||
Publisher: | ELSEVIER SCIENCE SA | ||||
ISSN: | 0022-328X | ||||
Official Date: | 15 June 2005 | ||||
Dates: |
|
||||
Volume: | 690 | ||||
Number: | 12 | ||||
Number of Pages: | 8 | ||||
Page Range: | pp. 2996-3003 | ||||
DOI: | 10.1016/j.jorgancjem.2005.03.026 | ||||
Publication Status: | Published |
Data sourced from Thomson Reuters' Web of Knowledge
Request changes or add full text files to a record
Repository staff actions (login required)
View Item |