dc.contributor.author |
Bowmaker, Graham |
en |
dc.contributor.author |
Boyd, Peter |
en |
dc.contributor.author |
CAMPBELL, GK |
en |
dc.contributor.author |
ZVAGULIS, M |
en |
dc.date.accessioned |
2011-09-14T22:07:28Z |
en |
dc.date.issued |
1986-06-01 |
en |
dc.identifier.citation |
J CHEM SOC DALTON 1065-1073 Jun 1986 |
en |
dc.identifier.issn |
0300-9246 |
en |
dc.identifier.uri |
http://hdl.handle.net/2292/7924 |
en |
dc.description.abstract |
The redox properties of nickel(II) and palladium(II) complexes of the type [M(M′S4)n(R2NCS2)2 –n]n–(n= 0–2, M = Ni or Pd, M′= Mo or W) have been studied using d.c. and a.c. cyclic voltammetry at a platinum electrode in dichloromethane solution. The series of complexes show initial reversible or quasi-reversible one-electron reduction to give species containing a single unpaired electron. E.s.r. spectra have been used to identify the species produced after one-electron reduction. In the case of palladium, the reduction potential increases smoothly with increasing n whilst the unpaired electron is increasingly delocalised from the central metal ion with decreasing g anisotropy. In contrast, the reduction potential of the nickel complexes increases sharply from n= 0 to 1 with a corresponding increase in the g anisotropy. The reduction potential increases again for n= 2, however the e.s.r. spectrum shows an unusual ‘reversal’ of g anisotropy (g‖ < g⊥) compared to that expected for a d9 planar complex with the unpaired electron in a nickel dxy orbital (g‖ > g⊥). It is suggested that in the case of n= 1 or 2 the unpaired electron is now occupying a molecular orbital composed of the low-lying molybdenum (or tungsten)d orbitals. This is supported by scattered wave Xα calculations of the electronic structure of the model complexes [Ni(H2NCS2)2], [Ni(MoS4)(H2NCS2)]– and [Ni(MoS4)2]2– and their oneelectron reduction products. |
en |
dc.language |
English |
en |
dc.publisher |
ROYAL SOC CHEMISTRY |
en |
dc.relation.ispartofseries |
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS |
en |
dc.rights |
Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated. Previously published items are made available in accordance with the copyright policy of the publisher. |
en |
dc.rights.uri |
https://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm |
en |
dc.subject |
Science & Technology |
en |
dc.subject |
Physical Sciences |
en |
dc.subject |
Chemistry, Inorganic & Nuclear |
en |
dc.subject |
Chemistry |
en |
dc.title |
ELECTRON-SPIN-RESONANCE STUDIES OF ONE-ELECTRON REDUCTION PRODUCTS OF NICKEL(II) AND PALLADIUM(II) COMPLEXES CONTAINING TETRATHIOMOLYBDATE, TETRATHIOTUNGSTATE, AND DIALKYLDITHIOCARBAMATE LIGANDS, "[M(M'S4)N(R2NCS2)2-N)]N-(N=0-2,M=NI OR PD,M'=MO OR W) |
en |
dc.type |
Journal Article |
en |
dc.identifier.doi |
10.1039/dt9860001065 |
en |
pubs.issue |
6 |
en |
pubs.begin-page |
1065 |
en |
dc.rights.holder |
Copyright: Royal Society of Chemistry |
en |
pubs.author-url |
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=A1986C869500002&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=6e41486220adb198d0efde5a3b153e7d |
en |
pubs.end-page |
1073 |
en |
dc.rights.accessrights |
http://purl.org/eprint/accessRights/RestrictedAccess |
en |
pubs.subtype |
Article |
en |
pubs.elements-id |
141851 |
en |
pubs.record-created-at-source-date |
2013-06-05 |
en |