Decomposition of tosylhydrazones of benzoin, benzoin acetate, and benzoin benzoate with alkali and metal complex hydrides

1996 ◽  
Vol 74 (2) ◽  
pp. 227-231 ◽  
Author(s):  
Tsukasa Iwadare ◽  
Yoshiyuki Ichinohe ◽  
Kazuhiko Orito
Keyword(s):  
Metal Complex ◽  
Key Words ◽  
Complex Hydrides ◽  
Trans Stilbene ◽  
Adjacent Group ◽  
Selective Formation

Treatment of tosylhydrazones of benzoin, benzoin acetate, and benzoin benzoate with alkali under protic and aprotic conditions yielded diphenyl acetylene together with desoxybenzoin. An increase in leaving aptitude of the adjacent group enhanced the formation of diphenyl acetylene. By treatment with LiAlH4 and with NaBH4, the tosylhydrazones gave stilbenes in good yields. Selective formation of cis- or trans-stilbene was observed in some cases. Key words: tosylhydrazone, benzoin derivatives, decomposition, metal complex hydrides.

The photochemistry of EDA complexes in micellar solutions. II. The stilbene–methylviologen system in the presence of oxygen

1991 ◽  
Vol 69 (1) ◽  
pp. 146-150 ◽  
Author(s):  
M. Hamity ◽  
R. H. Lema
Keyword(s):  
Sodium Dodecyl Sulfate ◽  
Key Words ◽  
Methyl Viologen ◽  
Sodium Dodecyl ◽  
Cation Radical ◽  
Reaction Scheme ◽  
Quantum Yields ◽  
Micellar Solutions ◽  
Trans Stilbene ◽  
Donor Acceptor

The photolyses of electron donor–acceptor (EDA) complexes formed between both cis-stilbene (cS) and trans-stilbene (tS) as donors and mefhylviologen (MV+2) as acceptor have been carried out in homogeneous ethanolic and in micellar sodium dodecyl sulfate (SDS) solutions, in the presence of oxygen. The stilbene loss quantum yields (Φ−S) have been determined in both media. Quantum yields were observed to be dependent upon methylviologen concentration and the acidity of media. A reaction scheme is proposed, which accounts for experimental results and can be related to the photochemistry of MV+2 and its cation radical MV•+. Key words: EDA complexes, micelles, methyl viologen, stilbene.

Metal-Complex Hydrides for Hydrogen-Storage Application

2005 ◽  
Vol 475-479 ◽  
pp. 2437-2440
Author(s):  
Xing Long Gou ◽  
Li Na Xu ◽  
Wei Yang Li ◽  
Jun Chen ◽  
Qiang Xu
Keyword(s):  
Hydrogen Storage ◽  
Metal Complex ◽  
Photoelectron Spectroscopy ◽  
Catalytic Mechanism ◽  
X Ray Diffraction ◽  
X Ray ◽  
Complex Hydrides ◽  
Transmission Electron ◽  
Dehydrogenation Kinetics ◽  
Transfer State

Metal-complex hydrides Li3AlH6 and V-doped Li3AlH6 nanoparticles were synthesized by solid reactions of LiH and LiAlH4 in the absence and in the presence of VCl3, respectively. X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, Brunauer- Emmett-Teller sorption, thermogravimetry and differential thermal analysis have been used to investigate the phase composition, microstructure and surface properties. Not only the nanocrystalline Li3AlH6, but also the coexisting catalyst with “valence-transfer” state can influence the dehydrogenation kinetics. The extension of the catalytic mechanism is attractive for reversible hydrogen storage of the alanate system.

Metal-Complex Hydrides for Hydrogen-Storage Application

2005 ◽  
pp. 2437-2440
Author(s):  
Xing Long Gou ◽  
Li Na Xu ◽  
Wei Yang Li ◽  
Jun Chen ◽  
Qiang Xu
Keyword(s):  
Hydrogen Storage ◽  
Metal Complex ◽  
Complex Hydrides

Synthesis of Metal Complex Hydrides for Hydrogen Storage

2007 ◽  
Vol 111 (40) ◽  
pp. 14917-14924 ◽  
Author(s):  
Jun Wang ◽  
Armin D. Ebner ◽  
James A. Ritter
Keyword(s):  
Hydrogen Storage ◽  
Metal Complex ◽  
Complex Hydrides

The properties of the metal complex hydrides

1979 ◽  
Vol 52 (2) ◽  
pp. 113-127 ◽  
Author(s):  
Rosanna Bonaccorsi ◽  
Eolo Scrocco ◽  
Jacopo Tomasi
Keyword(s):  
Metal Complex ◽  
Complex Hydrides

Graphyne and Graphdiyne: Versatile Catalysts for Dehydrogenation of Light Metal Complex Hydrides

2013 ◽  
Vol 117 (42) ◽  
pp. 21643-21650 ◽  
Author(s):  
Huize Yu ◽  
Aijun Du ◽  
Y. Song ◽  
Debra J. Searles
Keyword(s):  
Metal Complex ◽  
Light Metal ◽  
Complex Hydrides

C(2)-H isotopic exchange in coordinated imidazoles revisited. The case of the [Co(NH3)5ImH]3+ ion

1999 ◽  
Vol 77 (2) ◽  
pp. 178-181 ◽  
Author(s):  
Charles R Clark ◽  
Allan G Blackman ◽  
M Ross Grimmett ◽  
Akbar Mobinikhaledi
Keyword(s):  
Metal Complex ◽  
Temperature Dependence ◽  
Key Words ◽  
Rate Constant ◽  
Rate Constants ◽  
Isotopic Exchange ◽  
Ionization Constant ◽  
Ionization Constants ◽  
First Order ◽  
Acid Ionization

The temperature dependence of the acid ionization constants of [Co(NH3)5ImH]3+ in H2O (I = 1.0 M (NaClO4)): pKa (°C) = 10.10 ± 0.04 (25.0), 9.92 ± 0.03 (30.0), 9.82 ± 0.02 (35.0), 9.62 ± 0.03 (40.0), and [Co(ND3)5ImD]3+ in D2O (I = 0.35 M (NaClO4)): pKa (°C) = 10.58 ± 0.06 (25.0), 9.46 ± 0.08 (60.0) is reported. Observed first-order rate constants for H/D exchange at C-2 in [Co(ND3)5ImD]3+ over the pD range 8.08-11.20 (60.0°C, I = 0.35 M (NaClO4)) follow an equation of the form: kobs = kODKw/(aD+ + Ka)γ±, with kOD (0.27 ± 0.06 M-1 s-1) corresponding to the rate constant for OD--catalyzed abstraction of H-2 in [Co(ND3)5ImD]3+, and Ka ((2.8 ± 0.7) × 10-10 M, pKa = 9.55 ± 0.13) to the acid ionization constant of this species. No evidence was found for a pathway to H/D exchange in the imidazolate moiety of [Co(ND3)5Im]2+.Key words: kinetics, H/D-exchange, imidazole, metal complex.

Synthesis, electrochemical and spectroscopic investigations of 2,2′:4,4″-terpyridine and 2,2′:4,4″:6,2″-quaterpyridine ligands for metal complex photoelectrochemistry

1991 ◽  
Vol 69 (2) ◽  
pp. 315-321 ◽  
Author(s):  
L. Persaud ◽  
G. Barbiero
Keyword(s):  
Cyclic Voltammetry ◽  
Metal Complex ◽  
Key Words ◽  
Aldol Condensation ◽  
Electrochemical Behaviour ◽  
Condensation Reaction ◽  
Linear Sweep ◽  
Spectral Behaviour ◽  
Neutral Ligands ◽  
Electronic Spectral Behaviour

The synthesis of 2,2′:4,4″:6,2′″-quaterpyridine and 2,2′:4,4″-terpyridine was accomplished by a reverse aldol condensation reaction of the appropriate aldehyde with alkyl and pyridyl acetyls. A selective quaternization method in toluene is described. In this method the 1,1′ nitrogens survive alkylation and are free to coordinate with metals to form metal complexes. The electrochemical behaviour of the neutral ligands as well as the monoquaternized cations was established by linear sweep cyclic voltammetry. Spectroelectrochemical techniques were used to establish the electronic spectral behaviour and stability of the radicals obtained upon reduction. Key words: 2,2′:4,4″-terpyridine, quaterpyridine, selective quaternization.

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