Synthesis, characterization, and spectroscopy of dipyridocatecholate complexes of platinum

Journal Article · Wed May 21 04:00:00 EDT 1997 · Inorganic Chemistry

DOI:https://doi.org/10.1021/ic9610851· OSTI ID:563608

Paw, W; Eisenberg, R ^[1]

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1. Univ. of Rochester, NY (United States)

Several new complexes containing 1,10-phenanthroline-5,6-diolate (dipyridocatecholate, dpcat{sup 2-}) ligand are reported. The complex (dpcat)Pt(dbbpy) (4; dbbpy = di-tert-butylibipyridine) was synthesized from Cl{sub 2}Pt(dbbpy) and dpcat{sup 2-}. The reaction of (dpcat)Pt(dbbpy) with Cl{sub 2}Pt(PhCN){sub 2} yielded Cl{sub 2}pt(dpcat)Pt(dbbpy) (5). The latter complex was reacted with 3,4-dimercaptotoluene (toluenedithiolate, tdt{sup 2-}), 3,5-di-tert-butylcatecholate (dbcat{sup 2-}), and dpcat{sup 2-} to give (tdt)Pt(dpcat)pt(dbbpy) (6), (dbcat)Pt(dbbpy) (7), and (dpcat)Pt(dpcat)Pt(dpcat)Pt(dbbpy) (8), respectively. All of these complexes containing Pt(diimine)(diolate) centers display intense absorption bands in the 500-600 nm range. However, excitation at these wavelengths does not result in photoemission similar to that seen for closely related Pt(diimine)(dithiolate) complexes. The absorption bands of the dinuclear species are unsymmetrical, possibly indicating isolated but overlapping transitions for the two chromophores in each complex. The complex (dpcat)Pt(dbbpy) was found to react with (dbbpy){sub 2}RuCl{sub 2} and NH{sub 4}PF{sub 6} to yield [(dbbpy){sub 2}Ru(dpcat)-Pt(dbbpy)](PF{sub 6}){sub 2} (10). A connectivity structure of this compound confirms the structural arrangement and the role of dpcat as a bridging ligand between a square planar Pt(II) center and an octahedral Ru(II) moiety. In an analogous synthesis, the trinuclear complex [(dbbpy){sub 2}Ru(dpcat)Pt(dpcat)Pt(dbbpy)](PF{sub 6}){sub 2} (11) was obtained by reacting (dpcat)Pt(dbbpy) with (dbbpy){sub 2}RuCl{sub 2} and NH{sub 4}PF{sub 6}. The complex [(dbbpy){sub 2}Ru(dpcat)Pt(dbbpy)]-(PF{sub 6}){sub 2} displays absorption bands associated with individual Ru and Pt centers and photoemission that arises from Ru(diimine){sub 3}{sup 2+}. 25 refs., 3 figs., 2 tabs.

• OSTI ID: 563608
• Journal Information: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 11 Vol. 36; ISSN 0020-1669; ISSN INOCAJ
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
40 CHEMISTRY
ABSORPTION SPECTRA
ABSORPTION SPECTROSCOPY
BENZOQUINONES
CATECHOLAMINES
CHELATING AGENTS
CHEMICAL PROPERTIES
ELECTROCHEMISTRY
EXCITATION
LIGANDS
MOLECULAR STRUCTURE
NMR SPECTRA
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
PHOTOEMISSION
PHOTOLUMINESCENCE
PLATINUM COMPLEXES
REDUCTION
RUBIDIUM
STRUCTURAL CHEMICAL ANALYSIS
SYMMETRY
SYNTHESIS
WAVELENGTHS