Dimethylplatinum(Iv) complexes with cyanide: Thermal and photoassisted substitution reactions, and characterization of products by N.M.R.

Appleton T.G., Hall J.R. and Williams M.A. (1987) Dimethylplatinum(Iv) complexes with cyanide: Thermal and photoassisted substitution reactions, and characterization of products by N.M.R.. Australian Journal of Chemistry, 40 9: 1565-79. doi:10.1071/CH9871565


Author Appleton T.G.
Hall J.R.
Williams M.A.
Title Dimethylplatinum(Iv) complexes with cyanide: Thermal and photoassisted substitution reactions, and characterization of products by N.M.R.
Journal name Australian Journal of Chemistry   Check publisher's open access policy
ISSN 1445-0038
Publication date 1987-01-01
Sub-type Article (original research)
DOI 10.1071/CH9871565
Volume 40
Issue 9
Start page 1565
End page 79
Total pages -1485
Subject 1600 Chemistry
Abstract Reactions of cyanide with the dimethylplatinum(Iv) complexes, [PtMe2(OH)2(H2O)1·5]n, [PtMe2Br2]n and fac-PtMe2Br(H2O)3 +, have been studied, principally by 1H, 13C and 195Pt n.m.r. Cyanide rapidly displaces the ligands trans to the methyl groups. Subsequent reactions cis to the methyl groups occur more slowly with heating, or, for bromo complexes, on ultraviolet irradiation. These substitution reactions compete with reductive elimination of groups from the platinum(IV) compounds to produce platinum(II) products. All attempts to prepare solutions of fac-PtMe2(CN)(H2O)3 + were unsuccessful. Oxidative addition of ICN to cis-PtMe2(py)2 (py = pyridine) gave PtMe2I(CN)(py)2, from which a solution of fac-PtMe2(CN)(MeOH)3 + in methanol could be obtained. Addition of water or aqueous acid to this solution gave a very insoluble precipitate of [PtMe2(CN)(OH)]n The cis and trans influences on 1Jpt-C and δ C of the cyanide ligands have been evaluated.
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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