15N and 195Pt NMR spectra of platinum ammine complexes: Trans- and cis-influence series based on 195Pt-15N coupling constants and 15N chemical shifts

Appleton T.G., Hall J.R. and Ralph S.F. (1985) 15N and 195Pt NMR spectra of platinum ammine complexes: Trans- and cis-influence series based on 195Pt-15N coupling constants and 15N chemical shifts. Inorganic Chemistry, 24 26: 4685-4693.

Author Appleton T.G.
Hall J.R.
Ralph S.F.
Title 15N and 195Pt NMR spectra of platinum ammine complexes: Trans- and cis-influence series based on 195Pt-15N coupling constants and 15N chemical shifts
Journal name Inorganic Chemistry   Check publisher's open access policy
ISSN 0020-1669
Publication date 1985-01-01
Sub-type Article (original research)
Volume 24
Issue 26
Start page 4685
End page 4693
Total pages 9
Subject 1604 Human Geography
Abstract 195Pt and 15N NMR spectra have been obtained for the series of platinum(II) complexes Pt(15NH3)3Zn+, cis-Pt(15NH3)2Z2m+, and cis-Pt(15NH3)2YZm+ (Z, Y are neutral or anionic ligands) and for the platinum(IV) complexes derived from them by peroxide oxidation, mer-Pt(15NH3)3Z(OH)2 n+ and Pt(15NH3)2Z2(OH)2 m+. From the spectra of the triammineplatinum(II) complexes, the effects on δN and 1J(Pt-N) trans and cis to Z, and on δPt, of replacing one of the ammine ligands of Pt(15NH3)4 2+ by Z were measured. With the assumption that the effects of replacing two ammine ligands are additive, the NMR parameters for diammineplatinum(II) complexes were calculated. Agreement with experimental values was good overall. NMR data for the platinum(IV) complexes were treated similarly, again with good agreement between calculated and experimental values for the diammine complexes. The influence of different ligands Z on the NMR parameters for the two different oxidation states, while generally similar, did show some consistent differences in detail. The influences of the halide ions on δPt, and on δN and J(Pt-N) trans to Z, were greater for platinum(IV) relative to platinum(II). For the series Pt(15NH3)3Zn+, results are consistent with previous generalizations, that changes in δPt mainly depend on the influence of Z on Pt 5d orbitale (through involvement in the Pt-Z σ-bond and through splitting of the d-orbital energy levels) and that changes in J(Pt-N) trans to Z depend mainly on variations in the Pt 6s contribution to the Pt-N bond. δN trans to Z shows an inverse linear correlation with δPt. Cis influences on δN and J(Pt-N) are smaller than trans influences but are still significant.
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
Collection: Scopus Import - Archived
 
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