195Pt NMR of heteropolymetallic complexes containing secondary dithiooxamides as binucleating ligands

Santo Lanza; Giovanna Callipari; Frédérique Loiseau; Scolastica Serroni; Giuseppe Tresoldi

doi:10.1021/ic0507215

195Pt NMR of heteropolymetallic complexes containing secondary dithiooxamides as binucleating ligands

Inorg Chem. 2005 Sep 19;44(19):6717-24. doi: 10.1021/ic0507215.

Authors

Santo Lanza¹, Giovanna Callipari, Frédérique Loiseau, Scolastica Serroni, Giuseppe Tresoldi

Affiliation

¹ Dipartimento di Chimica Inorganica, Chimica Analitica e Chimica Fisica, Villaggio S. Agata, Salita Sperone 31, 98166 Messina, Italy. lanza@chem.unime.it

PMID: 16156630
DOI: 10.1021/ic0507215

Abstract

Monometallic [Pt{S-S2C2(NR)2H}2] (S-S2C2(NR)2H = kappa2-S,S-S2C2(NR)2H = bis-dialkyl-dithioxamidate, R = methyl, isoamyl, benzyl) and binuclear and trinuclear heterobimetallic complexes [Pt{S-S2C2(NR)2H}{mu-S2C2(NR)2}MLn] (mu-S2C2(NR)2 = kappa2-S,S(Pt)-kappa2-N,N(M)-S2C2(NR)2) and [Pt{{mu-S2C2(NR)2}MLn}2] (MLn+ = [(eta3-allyl)palladium]+, [bis-(2-phenylpyridine)rhodium]+, [(eta6-p-cymene)(chloro)ruthenium]+, [(1,4-cyclooctadiene)rhodium]+, [(pentamethylcyclopentadienyl)(chloro)rhodium]+) have been prepared and characterized. The progressive substitution of the residual amidic hydrogen in the [Pt{S-S2C2(NR)2H}2] complexes with a MLn+ metal fragment results in the deshielding of platinum nuclei, a red shift of the MLCT absorption maximum, and a decrease in the oxidation potential. Such behavior has been interpreted as a progressive electron shift from platinum to the binucleating ligands, the extent of which depends on the nature of MLn+ metal fragment.