Multinuclear N.M.R. study of some Di- and Tri-methylplatinum(IV) complexes

Agnew N.H., Appleton T.G. and Hall J.R. (1982) Multinuclear N.M.R. study of some Di- and Tri-methylplatinum(IV) complexes. Australian Journal of Chemistry, 35 5: 881-894. doi:10.1071/CH9820881

Author Agnew N.H.
Appleton T.G.
Hall J.R.
Title Multinuclear N.M.R. study of some Di- and Tri-methylplatinum(IV) complexes
Journal name Australian Journal of Chemistry   Check publisher's open access policy
ISSN 1445-0038
Publication date 1982-01-01
Sub-type Article (original research)
DOI 10.1071/CH9820881
Volume 35
Issue 5
Start page 881
End page 894
Total pages 14
Subject 1600 Chemistry
Abstract The 13C n.m.r. spectrum of the dimer [PtMe2Br(MeOH)(μ-OH)]2, formed by dissolving the complex [PtMe2Br(OH)]., in methanol, has been analysed, to give 2JPt-o-Pt 103·6 Hz. 1H and 1H-decoupled 195Pt spectra show complex patterns owing to superposition of spectra from different isotopomers. By contrast, solutions of [PtMe2Br2]., in methanol, which contain monomeric PtMe2Br2(MeOH)2, give simple spectra. [PtMe2Br(OH)]n dissolves in dilute aqueous KOH solution at pH 9 to give a solution containing the ‘inert’ dimer [PtMe2Br(OH)(μ-OH)]2 2-. Other species are present at higher pH, but the solution never contains simple PtMe2Br(OH)3 2- alone. Dissolution of [PtMe2(OH)2(H2O)1.5]., in alkali at pH 12 gives a dimer [PtMe2Br(OH)(μ-OH)]2 2_ whose 13C n.m.r. spectrum has been analysed to give 2JPt-o-Pt 123·5 Hz. Progressive substitution of water in fac-PtMe3(H2O)3 + by pyridine causes regular 195Pt shifts to lower frequency. 195Pt, 13C and 1H data indicate that fac-PtMe3X3 2- exist as simple anions for X = NO2, CN, but not for X = NCS. 195Pt chemical shifts of di- and tri-methylplatinum(iv) complexes are discussed. The hydroxo- bridged dimers resonate at higher frequencies than monomeric complexes, owing to strain in the four-membered Pt(OH)2Pt rings, 1JPt-C is much more sensitive to the cis influence than 2JPt-CH3.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
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