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Inter- and intra-molecular condensation patterns of (en)PdII with trans-[a2PtL2]2+ (a = am(m)ine, L = 2-aminopyridine): PtPd3 and Pt2Pd4 species with multiple amide bridges. Unexpected trapping of a pair of nitrate ions by a Pt2Pd4 double cone


Beck, Bettina; Schneider, Alexandra; Freisinger, Eva; Holthenrich, Dagmar; Erxleben, Andrea; Albinati, Alberto; Zangrando, Ennio; Randaccio, Lucio; Lippert, Bernhard (2003). Inter- and intra-molecular condensation patterns of (en)PdII with trans-[a2PtL2]2+ (a = am(m)ine, L = 2-aminopyridine): PtPd3 and Pt2Pd4 species with multiple amide bridges. Unexpected trapping of a pair of nitrate ions by a Pt2Pd4 double cone. Dalton Transactions, (12):2533-2539.

Abstract

Reaction of trans-[a2Pt(Hampy)2]X2 (a = NH3, 2; a = MeNH2, 3; Hampy = 2-aminopyridine; X = NO3 or ClO4) with an excess of [(en)Pd(H2O)2]2+ in aqueous solution leads to two types of condensation products: (i) tetranuclear PtPd3 species, in which the deprotonated “a” ligands (μ-NH2, μ-MeNH) and the deprotonated amino group of the 2-aminopyridine (ampy) ligands are chelated by two (en)PdII entities and in addition a single PdII ion (without en) cross-links the amido functions of ampy in a nearly linear fashion. The four metal ions thus form a diamond arrangement with a short (<2.5 Å) Pt→Pd dative bond. (ii) Hexanuclear Pt2Pd4 species, in which (en)PdII moieties bridge exclusively amido groups of four ampy ligands in such a way that an open rectangular box (or double cone) is formed. This allows two nitrate counter ions to become inserted in the cavity of the +8 charged cation. Thus in both cases the ampy ligand acts as a μ3-ligand, either in an intramolecular or an intermolecular fashion.

Abstract

Reaction of trans-[a2Pt(Hampy)2]X2 (a = NH3, 2; a = MeNH2, 3; Hampy = 2-aminopyridine; X = NO3 or ClO4) with an excess of [(en)Pd(H2O)2]2+ in aqueous solution leads to two types of condensation products: (i) tetranuclear PtPd3 species, in which the deprotonated “a” ligands (μ-NH2, μ-MeNH) and the deprotonated amino group of the 2-aminopyridine (ampy) ligands are chelated by two (en)PdII entities and in addition a single PdII ion (without en) cross-links the amido functions of ampy in a nearly linear fashion. The four metal ions thus form a diamond arrangement with a short (<2.5 Å) Pt→Pd dative bond. (ii) Hexanuclear Pt2Pd4 species, in which (en)PdII moieties bridge exclusively amido groups of four ampy ligands in such a way that an open rectangular box (or double cone) is formed. This allows two nitrate counter ions to become inserted in the cavity of the +8 charged cation. Thus in both cases the ampy ligand acts as a μ3-ligand, either in an intramolecular or an intermolecular fashion.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Language:English
Date:2003
Deposited On:27 Jun 2012 11:30
Last Modified:05 Apr 2016 15:40
Publisher:Royal Society of Chemistry
ISSN:1477-9226
Additional Information:Electronic supplementary information (ESI) available: 1H NMR spectra of 2a, 4a and 5; views of the crystal structure of 5. See http://www.rsc.org/suppdata/dt/b3/b301708g/.
Free access at:Publisher DOI. An embargo period may apply.
Publisher DOI:https://doi.org/10.1039/B301708G

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