Inter- And Intra-Molecular Condensation Patterns Of (En)Pd-Ii With Trans-[A(2)Ptl(2)](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(2003)

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摘要
Reaction of trans-[a(2)Pt(Hampy)(2)] X-2 (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 (mu-NH2, mu-MeNH) and the deprotonated amino group of the 2-aminopyridine (ampy) ligands are chelated by two (en) Pd-II entities and in addition a single Pd-II 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 angstrom) Pt-->Pd dative bond. (ii) Hexanuclear Pt2Pd4 species, in which (en) Pd-II 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 mu(3)-ligand, either in an intramolecular or an intermolecular fashion.
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crystal structure
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