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Crystal structure and dynamic behavior of [Ni{PhNHC(S)NP(S)(OPr i)2-S,S}2] complex in dichloromethane solution
Authors
Brusko V.
Krivolapov D.
+4 more
Litvinov I.
Rakhmatullin A.
Shtyrlin V.
Zabirov N.
Publication date
1 January 2006
Publisher
Abstract
The crystal structure of the complex [Ni{PhNHC(S)NP(S)(OPr i)2-S,S}2] has been determined and its behavior in dichloromethane solution investigated by NMR 31P spectroscopy. The X-ray structural analysis shows the nickel atom at the symmetry center in a distorted square-planar arrangement with trans-disposition of the ligands. The six-membered cycle NiS(1)PNCS(2) has the form of the asymmetric boat. In dichloromethane solutions of the compound four signals have been detected by 31P-{1H} NMR method. These signals are related to three diamagnetic square-planar isomers with different dispositions and conformations of two ligands in anti-orientation: trans-chair-boat (A), cis-boat-boat (B), and trans-boat-boat (C). These isomers are in slow exchange equilibria. It was shown that all these forms are in rather fast chemical exchange with minor (unobserved) paramagnetic pseudo-tetrahedral isomers (AT, B T, and CT). The thermodynamic constants of equilibria between A, B, and C as well as rate constants and activation parameters for conversion of three square-planar to respective pseudo-tetrahedral forms were calculated from the 31P-{1H} NMR data. © 2005 Elsevier Ltd. All rights reserved
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Kazan Federal University Digital Repository
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oai:dspace.kpfu.ru:net/95778
Last time updated on 07/05/2019
Kazan Federal University Digital Repository
See this paper in CORE
Go to the repository landing page
Download from data provider
oai:dspace.kpfu.ru:net/136798
Last time updated on 07/05/2019