Hydrogen atom abstraction from C-H, P-H, Si-H, and Sn-H bonds by the triplet excited state of the tetrakis(. mu. -pyrophosphito)diplatinum(II) tetraanion. Spectroscopic observation of the mixed-valence hydride complexes Pt/sub 2/(. mu. -P/sub 2/O/sub 5/H/sub 2/)/sub 4/H/sup 4 -/

Journal Article · Wed Sep 30 00:00:00 EDT 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00254a028· OSTI ID:6089809

Roundhill, D M; Atherton, S J; Shen, Z

Pulse radiolysis of aqueous solutions of Pt/sub 2/(..mu..-P/sub 2/O/sub 5/H/sub 2/)/sub 4//sup 4 -/ at pH 4 with added t-BuOH gives Pt/sub 2/(..mu..-P/sub 2/O/sub 5/H/sub 2/)/sub 4/H/sup 4 -/ via reaction with an electron and a proton. Pulsed-laser photolysis (Nd-YAG at 355 nm) of aqueous solutions of Pt/sub 2/(..mu..-P/sub 2/O/sub 5/H/sub 2/)/sub 4//sup 4 -/ with added isopropyl alcohol, phosphorus acid, or hypophosphorous acid also gives Pt/sub 2/(..mu..-P/sub 2/O/sub 5/H/sub 2/)/sub 4//sup 4 -/ by hydrogen atom abstraction. The mixed-valence hydride is similarly formed in methanolic solutions of (PPN)/sub 4/(Pt/sub 2/(..mu..-P/sub 2/O/sub 5/H/sub 2/)/sub 4/) from added triethylsilane or tributyltin hydride. The intermediacy of the Me/sub 2/COH radical is evidenced by the formation of both pinacol and acetone in the photochemically catalyzed dehydrogenation of isopropyl alcohol with Pt/sub 2/(..mu..-P/sub 2/O/sub 5/H/sub 2/)/sub 4//sup 4 -/ in aqueous solution. The other radical, Pt/sub 2/(..mu..-P/sub 2/O/sub 5/H/sub 2/)/sub 4/H/sup 4 -/, disproportionates to Pt/sub 2/(..mu..-P/sub 2/O/sub 5/H/sub 2/)/sub 4/H/sub 2//sup 4 -/ and Pt/sub 2/(..mu..-P/sub 2/O/sub 5/H/sub 2/)/sub 4//sup 4 -/. The Bu/sub 3/Sn radical has been detected by transient difference laser spectroscopy in solutions containing Pt/sub 2/(..mu..-P/sub 2/O/sub 5/H/sub 2/)/sub 4/H/sub 2//sup 4 -/ and Bu/sub 3/SnH. The quenching rates for hydrogen atoms donors with the /sup 3/A/sub 2u/ state of Pt/sub 2/(..mu..-P/sub 2/O/sub 5/H/sub 2/)/sub 4//sup 4 -/*, as measured by the Stern-Volmer equation, are given and compared.

• Research Organization: Tulane Univ., New Orleans, LA
• OSTI ID: 6089809
• Journal Information: J. Am. Chem. Soc.; (United States), Vol. 109:20
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
08 HYDROGEN
HYDRIDES
CHEMICAL PREPARATION
PHOSPHINES
EXCITED STATES
PHOTOLYSIS
RADIOLYSIS
PLATINUM COMPOUNDS
ABSORPTION SPECTROSCOPY
ANIONS
AQUEOUS SOLUTIONS
CHEMICAL REACTION KINETICS
EXPERIMENTAL DATA
HYDROGEN
PHOTOCHEMISTRY
RADICALS
REACTION INTERMEDIATES
TRIPLETS
VALENCE
CHARGED PARTICLES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DECOMPOSITION
DISPERSIONS
ELEMENTS
ENERGY LEVELS
HYDROGEN COMPOUNDS
INFORMATION
IONS
KINETICS
MIXTURES
MULTIPLETS
NONMETALS
NUMERICAL DATA
PHOSPHORUS COMPOUNDS
PHOTOCHEMICAL REACTIONS
RADIATION CHEMISTRY
RADIATION EFFECTS
REACTION KINETICS
SOLUTIONS
SPECTROSCOPY
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
400500* - Photochemistry
400600 - Radiation Chemistry
080106 - Hydrogen- Production- Biosynthesis & Photochemical Processes