New mixed metal chain complexes of platinum(II) with copper(II), cobalt(II), nickel(II), zinc(II), uranium(VI), and thorium(IV) having substituted phosphonito groups as bridging ligands

Journal Article · Sat Oct 01 00:00:00 EDT 1977 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic50176a038· OSTI ID:7282955

Sperline, R P; Roundhill, D M

Complexes PtCl(OP(OMe)/sub 2/)(HOP(OMe)/sub 2/)L (L = PEt/sub 3/, PPh/sub 3/) are acidic and the proton bonded to oxygen can be removed by titration with sodium methoxide or 1,5-diazabicyclo(4.3.0)non-5-ene. The resulting anionic compound will chelate to copper(II), cobalt(II), dioxouranium(VI), and thorium(IV) through the oxygens to give mixed metal compounds (PtCl(OP(OR)/sub 2/)/sub 2/L)/sub n/M (n = 2, R = Me, L = PEt/sub 3/, M = Cu, UO/sub 2/ and L = PPh/sub 3/, M = Co; n = 2, R = Ph, L = PEt/sub 3/, M = Cu; n = 4, R = Me, L = PPh/sub 3/, M = Th). The complex PtCl(OP(OMe)/sub 2/)(F/sub 2/BOP(OMe)/sub 2/)PEt/sub 3/ can be prepared by treating PtCl(OP(OMe)/sub 2/)(HOP(OMe)/sub 2/)PEt/sub 3/ with BF/sub 3/ . Et/sub 2/O. Mixed metal trimetallic compounds are also obtained by treating the compounds Pt(OP(OMe)/sub 2/)/sub 2/(L--L) with the appropriate metal salt (L--L = 1,2-bis(diphenylphosphino)ethane (dppe), o-phenylenebis(dimethylarsine)(diars)). Complexes ((Pt(OP(OMe)/sub 2/)/sub 2/(L--L))/sub 2/M)(ClO/sub 4/)/sub 2/ (M = Cu, Zn, L--L = dppe, diars; M = Ni, Co, L--L = dppe) have been prepared. Electronic spectra of the mixed metal complexes show a square-planar geometry about copper (II) and nickel(II) and a tetrahedral geometry about cobalt(II). The cobalt(II) complexes show unusually low extinction coefficients for the visible and near-infrared bands, although with Racah parameter B values in the 650--700-cm/sup -1/ range the explanation for the low extinction coefficients is likely distortion rather than highly ionic character about Co(II).

• Research Organization: Washington State Univ., Pullman
• OSTI ID: 7282955
• Journal Information: Inorg. Chem.; (United States), Vol. 16:10
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
COBALT COMPLEXES
CHEMICAL PREPARATION
MAGNETIC MOMENTS
COPPER COMPLEXES
THORIUM COMPLEXES
URANIUM COMPLEXES
CHELATES
ELECTRON SPIN RESONANCE
LIGANDS
ORGANIC PHOSPHORUS COMPOUNDS
PLATINUM COMPLEXES
STEREOCHEMISTRY
ACTINIDE COMPLEXES
COMPLEXES
MAGNETIC RESONANCE
ORGANIC COMPOUNDS
RESONANCE
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties
400702 - Radiochemistry & Nuclear Chemistry- Properties of Radioactive Materials