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Synthesis and coordination chemistry of 1-phenyl-1-phospha-4,7-dithiacyclononane

Blower, Philip J., Chadwick, Alan V., Jeffery, John C., Mullen, Gregory E. D., Powell, Anne K., Salek, Spencer N., Smith, Raymond J., Went, Michael J. (1999) Synthesis and coordination chemistry of 1-phenyl-1-phospha-4,7-dithiacyclononane. Inorganica Chimica Acta, 294 (2). pp. 170-178. ISSN 0020-1693. (doi:10.1016/S0020-1693(99)00206-6) (The full text of this publication is not currently available from this repository. You may be able to access a copy if URLs are provided) (KAR id:17092)

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Reaction of PhP(CH2CH2SH)(2) with 1,2-dichloroethane and Cs2CO3 under high dilution conditions affords 1-phenyl-1-phospha-4,7-dithiacyclononane (L) as an oil in 52% yield. The geometry of L has been probed by H-1 NMR spectroscopy, which indicates an equilibrium mixture containing gauche S-C-C-S and S-C-C-P segments, and molecular mechanics calculations which find a lowest energy endodentate conformation minimum and also energetically accessible exodentate minima. Endo- and exodentate conformations are observed in the crystal structure of [Cu(eta(1)-L)(eta(3)-L)][PF6] (1) formed by the reaction of L with [Cu(NCMe)(4)[PF6]. Reaction of Hg(ClO4)(2) with L affords [HgL2][ClO4](2) (2) whose structure has also been established by X-ray diffraction. The mercury ion is in a very distorted octahedral environment with two short Hg-P bonds (average 2.404 Angstrom) and four long Hg-S bonds (average 3.092 Angstrom). Reaction of L with AgBF4 or Ni(BF4)(2) or CoBr2 or Fe(BF4)(2) affords [AgL2][BF4] (3), [NiL2][BF4](2), (4), [CoL2]BL2 (5) and FeL2][BF4](2) (6), respectively, which were characterised by FAB mass spectroscopy and elemental analysis. Cyclic voltammetry studies were used to compare the redox properties of 4, 5 and 6 with their trithiacyclononane (9S3) analogues and in compound 4 the ligand L was found to stabilise Ni in the oxidation states 0, I, Il and III. UV-Vis spectroscopic measurements show that L is a stronger field ligand than 9S3. EXAFS studies were also performed on 4, 5 and 6, which established that all three complexes are six-coordinate. (C) 1999 Elsevier Science S.A. All rights reserved.

Item Type: Article
DOI/Identification number: 10.1016/S0020-1693(99)00206-6
Uncontrolled keywords: Copper complexes; Nickel complexes; Phosphathiamacrocycle complexes; Thioether complexes
Subjects: Q Science > QD Chemistry
Q Science > QC Physics
Divisions: Divisions > Division of Natural Sciences > Biosciences
Depositing User: M. Nasiriavanaki
Date Deposited: 11 Jul 2009 10:20 UTC
Last Modified: 16 Nov 2021 09:55 UTC
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