Loughborough University
Leicestershire, UK
LE11 3TU
+44 (0)1509 263171
Loughborough University

Loughborough University Institutional Repository

Please use this identifier to cite or link to this item: https://dspace.lboro.ac.uk/2134/11236

Title: Dithioimidophosphinates and related systems
Authors: Birdsall, David J.
Issue Date: 1999
Publisher: © D. J. Birdsall
Abstract: The condensation reaction of iPr2PCl with hexamethyldisilazane, HN(SiMe3)2, followed by oxidation with sulfur, selenium or hydrogen peroxide yields Pr2P(E)NHP(E'),iPr2, where E = S, Se or 0. Single crystal X-ray experiments give a hydrogen bonded chain in all cases. Analogous PhO, EtO, Et and Ph substituted compounds were synthesised via condensation reactions between R2P(S)NH2 and R'P(S)CI yielding R2P(S)NHP(S)R'2 (R =PhO, Ph; R' = iPr, Et, EtO). Further crystallographic studies revealed iPr2P(S)NHP(S)(OPh)2 and Et2P(S)NHP(S)Ph2 to be hydrogen bonded dimers and iPr2P(S)NHP(S)Ph2 and Et2P(S)NHP(S)(OPh)2 to be hydrogen bonded chains. Reacting these compounds with Zn, Cd, Pd and Pt chlorides led to the formation of tetrahedral and square planar coordination complexes. Crystallographic studies on the complexes of R2P(E)NHP(E')R'2 revealed surprising ME2P2N ring geometries, some adopting pseudo "boat" conformations and others adopting pseudo "chair" conformation. Reactions of R2P(S)NHP(S)R'2 with CuC12 yielded trimeric copper(I) complexes of the type CU3[R2P(S)NP(S)R' 2]3. The trimeric system was found to be fluxional in solution. Crystallographic studies on the complexes show the trimer to have CU3S3 core. Further reactions of R2P(S)NHP(S)R' 2 with various tellurium (H) and (IV) salts yielded complexes of the types Te[R2P(S)NP(S)R' 2]2 and Te[R2P(S)NP(S)R' 2]Cl2,C6H4.0CH3. Crystallographic studies on the complexes show the tellurium to adopt pseudo two coordinate, four coordinate (square planar) and five coordinate (square based pyramid) arrangements. Tetradentate ligands of the type R2P(S)NHP(S)Ph(CH2)3P(S)PhNHP(S)R2 (where R = Ph or OPh) were synthesised by the condensation of NH2P(S)Ph(CH2)3P(S)PhNH2 with R2P(S)CI. Preliminary coordination studies suggest the formation of ML complexes were M = Zn, Cd and Ni. Molecular modelling techniques were used to investigate the optimum size of the "spacer groups" which links the two dithioimidophosphinate ligands. Using MNDOd and DFT optimisations, and with comparison to unlinked examples, the size of the ideal group was determined with respect to each particular metal.
Description: A Doctoral Thesis. Submitted in partial fulfilment of the requirements for the award of Doctor of Philosophy of Loughborough University.
URI: https://dspace.lboro.ac.uk/2134/11236
Appears in Collections:PhD Theses (Chemistry)

Files associated with this item:

File Description SizeFormat
Thesis-1999-Birdsall.pdf3.47 MBAdobe PDFView/Open
Form-1999-Birdsall.pdf46.27 kBAdobe PDFView/Open


SFX Query

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