Amide complexes of (diethylenetriamine)platinum(II)

Woon T.C. and Fairlie D.P. (1992) Amide complexes of (diethylenetriamine)platinum(II). Inorganic Chemistry, 31 20: 4069-4074. doi:10.1021/ic00046a016


Author Woon T.C.
Fairlie D.P.
Title Amide complexes of (diethylenetriamine)platinum(II)
Journal name Inorganic Chemistry   Check publisher's open access policy
ISSN 0020-1669
Publication date 1992-01-01
Year available 1992
Sub-type Article (original research)
DOI 10.1021/ic00046a016
Open Access Status Not yet assessed
Volume 31
Issue 20
Start page 4069
End page 4074
Total pages 6
Place of publication WASHINGTON
Publisher AMER CHEMICAL SOC
Language eng
Subject 1604 Human Geography
Abstract The coordination of acetamide and formamide to dienPtII is described. Both O- and N-bonded amide complexes are stable and have been isolated. As oxygen donor ligands for dienPtII, the binding affinity of amides lies between water and the very weakly coordinating acetone. The O-bonded amide complexes [dienPtOC(R)NH2]2+ are the kinetically preferred isomers in acetone but they rearrange very slowly (t1/2 ∼ 30 h, 20°C) and intramolecularly to the thermodynamically more stable N-bonded amide complexes (K = [N]/[O] ∼ 30). This is the reverse of relative amide affinities for harder metal ions (e.g. (NH3)5M3+, M = Co(III), Cr(III), Ru(III)) despite comparable polarizing power for dienPtII. The N-bonded amide isomers exist in solution (acetone, DMSO, water) as the imidol, [dienPtNH=C(OH)R]2+, rather than the amide tautomer, [dienPtNH2COR]2+, whereas the opposite has been observed for N-bonded ureas. The N-bonded amides adopt only one of the two possible geometric isomers which could result from restricted rotation about the amide N=C bond, and they are appreciably acidic (pKa 3.8, 20°C, H2O, I = 0.1 M; R = Me). Complexes of both O- and N-bonded amides are unstable in coordinating solvents (f1/2 < 1 min, O-isomers; t1/2 > 40 h, N-isomers; 20°C, H2O), but no decomposition of the amide ligands was detected during solvolysis (amide release) in either DMSO or water, nor was the Pt(II) susceptible to aerial oxidation as reported for mixtures of amides with cis-diammineplatinum(II). Coordination preferences of amides to "soft" versus "hard" metals are compared.
Keyword Chemistry, Inorganic & Nuclear
Chemistry
CHEMISTRY, INORGANIC & NUCLEAR
Q-Index Code C1
Institutional Status Unknown

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