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Title: 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

Abstract

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 lowmore » 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).« less

Authors:
;
Publication Date:
Research Org.:
Washington State Univ., Pullman
OSTI Identifier:
7282955
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorg. Chem.; (United States); Journal Volume: 16:10
Country of Publication:
United States
Language:
English
Subject:
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

Citation Formats

Sperline, R.P., and Roundhill, D.M. 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. United States: N. p., 1977. Web. doi:10.1021/ic50176a038.
Sperline, R.P., & Roundhill, D.M. 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. United States. doi:10.1021/ic50176a038.
Sperline, R.P., and Roundhill, D.M. Sat . "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". United States. doi:10.1021/ic50176a038.
@article{osti_7282955,
title = {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},
author = {Sperline, R.P. and Roundhill, D.M.},
abstractNote = {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).},
doi = {10.1021/ic50176a038},
journal = {Inorg. Chem.; (United States)},
number = ,
volume = 16:10,
place = {United States},
year = {Sat Oct 01 00:00:00 EDT 1977},
month = {Sat Oct 01 00:00:00 EDT 1977}
}