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Platinum and palladium bis(diphenylphosphino)ferrocene (dppf) complexes with heterocyclic N-acetamide ligands : synthesis and molecular structures of [MCl(sac)(κ2-dppf)] (M=Pt, Pd, sac=saccharinate), [PtCl(ata)(κ2-dppf)] and [Pt(ata)2(κ2-dppf)] (ataH=N-(2-thiazolyl)acetamide)
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Al-Jibori, Subhi A., Al-Nassiry, Amina I. A., Hogarth, Graeme and Salassa, Luca (2013) Platinum and palladium bis(diphenylphosphino)ferrocene (dppf) complexes with heterocyclic N-acetamide ligands : synthesis and molecular structures of [MCl(sac)(κ2-dppf)] (M=Pt, Pd, sac=saccharinate), [PtCl(ata)(κ2-dppf)] and [Pt(ata)2(κ2-dppf)] (ataH=N-(2-thiazolyl)acetamide). Inorganica Chimica Acta, Volume 398 . pp. 46-53. doi:10.1016/j.ica.2012.12.010 ISSN 0020-1693.
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Official URL: http://dx.doi.org/10.1016/j.ica.2012.12.010
Abstract
Room temperature addition of sodium saccharinate, Na(sac), to [MCl2(κ2-dppf)] (M = Pd, Pt; dppf = 1,1′-bis(diphenylphosphino)ferrocene) results in the formation of [MCl(sac)(κ2-dppf)] in which the sac ligand is coordinated in a monodentate fashion through nitrogen. All attempts to coordinate a second saccharinate ligand were unsuccessful. In contrast, reaction of [PtCl2(κ2-dppf)] with N-(2-thiazolyl)acetamide (ataH) in the presence of KOH results in successive replacement of both chlorides affording [PtCl(ata)(κ2-dppf)] and [Pt(ata)2(κ2-dppf)]. Crystal structures have determined for all four complexes. In both saccharinate complexes and [PtCl(ata)(κ2-dppf)] the heterocyclic amide ligand is coordinated as expected through the amide-nitrogen. In contrast in Pt(ata)2(κ2-dppf) both ligands are bound through the nitrogen atom of the thiazole ring. In order to understand the adoption of these different ligand binding modes, geometry optimization calculations were carried out on different isomers of both ata complexes. For [PtCl(ata)(κ2-dppf)] an energy difference of 10.5 kJ mol−1 was found between observed and unobserved isomers, while for [Pt(ata)2(κ2-dppf)] the difference was 9.3 kJ mol−1. The reasons for the adoption of these different coordination modes are not clear but steric factors are likely to be a major contributory factor.
Item Type: | Journal Article | ||||
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Physics | ||||
Journal or Publication Title: | Inorganica Chimica Acta | ||||
Publisher: | Elsevier Science BV | ||||
ISSN: | 0020-1693 | ||||
Official Date: | 2013 | ||||
Dates: |
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Volume: | Volume 398 | ||||
Page Range: | pp. 46-53 | ||||
DOI: | 10.1016/j.ica.2012.12.010 | ||||
Status: | Peer Reviewed | ||||
Publication Status: | Published | ||||
Access rights to Published version: | Restricted or Subscription Access |
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