METALLOCENE CHEMISTRY—A DECADE OF PROGRESS

1963 ◽  
Vol 41 (5) ◽  
pp. 1289-1314 ◽  
Author(s):  
M. D. Rausch
Keyword(s):  
Transition Metals ◽  
Arene Complexes ◽  
Aromatic System ◽  
Substitution Reactions ◽  
The Past ◽  
Orientation Effects ◽  
Oxidation Reduction ◽  
Carbonium Ions ◽  
Rearrangement Reactions ◽  
Derivatives Of

One of the most significant new frontiers in chemistry during the past decade has been the stabilization and study of π-organic derivatives of the transition metals. Over 60 elements are now known to form one or more cyclopentadienyl compounds. The aromatic-type reactions displayed by ferrocene and related complexes have also been extensively investigated. Ferrocene will undergo alkylation, acylation, sulphonation, metalation, arylation, formylation, aminomethylation, and other reactions characteristic of a highly reactive aromatic system. π-Cyclopentadienyl derivatives of vanadium, chromium, manganese, ruthenium, and osmium as well as certain π-arene complexes of chromium exhibit ring substitution reactions in varying degrees. Other metallocenes undergo ring addition reactions.The orientation effects of substituents on reactions of substituted ferrocenes have been studied. A variety of unique oxidation, reduction, dehydration, and rearrangement reactions are known in metallocene chemistry. Haloferrocenes and mercuriferrocenes are readily converted to biferrocenyl. Recent rate investigations have established that carbonium ions adjacent to metallocene nuclei possess unusual stabilization as a result of direct metal participation.

Theoretical study of the electron structure and properties of dithiocarbamates and their complexes with transition metals

1984 ◽  
Vol 49 (12) ◽  
pp. 2744-2750 ◽  
Author(s):  
Stanislav Miertuš ◽  
Vladimír Frecer
Keyword(s):  
Transition Metals ◽  
Theoretical Study ◽  
Electron Structure ◽  
Structure And Properties ◽  
Spin Multiplicity ◽  
Model Complexes ◽  
Oxidation Reduction ◽  
Bonding Properties ◽  
Derivatives Of

The semiempirical CNDO/2 method was used to calculate the electron structure of derivatives of dithiocarbamates, R2N-CS2, as anions and radicals. We studied changes in the oxidation-reduction and bonding properties by changes of R = H, CH2, C2H5, C3H5. Calculations were also carried out on model complexes of R2N-CS2 with metals Cu, Mn, Fe, Co, Ni. Differences in the electron structure of these complexes with various numbers of ligands, various states of oxidation and varying spin multiplicity of the central atoms were evaluated.

Fluorinated tricyclic neuroleptics with prolonged action: 8-Methoxy, 8-ethoxy, 8-ethylthio and 8-hydroxy derivatives of 3-fluoro-10-(4-methylpiperazino)-10,11-dihydrodibenzo[b,f]thiepin

1982 ◽  
Vol 47 (5) ◽  
pp. 1382-1391 ◽  
Author(s):  
Jiří Jílek ◽  
Josef Pomykáček ◽  
Jiřina Metyšová ◽  
Miroslav Protiva
Keyword(s):  
Acetic Acid ◽  
Polyphosphoric Acid ◽  
Prolonged Action ◽  
Substitution Reactions ◽  
Methoxy Derivative ◽  
Chloro Derivatives ◽  
Boron Tribromide ◽  
Derivatives Of ◽  
Central Depressant ◽  
Boiling Toluene

Acids IIa-c were prepared by reactions of (4-fluoro-2-iodophenyl)acetic acid with 4-methoxythiophenol, 4-ethoxythiophenol and 4-(ethylthio)thiophenol and cyclized with polyphosphoric acid in boiling toluene to dibenzo[b,f]thiepin-10(11H)-ones IIIa-c. Reduction with sodium borohydride afforded the alcohols IVa-c which were treated with hydrogen chloride and gave the chloro derivatives Va-c. Substitution reactions with 1-methylpiperazine resulted in the title compounds Ia-c out of which the methoxy derivative Ia was transformed by demethylation with boron tribromide to the phenol Id. Compounds Ia-d are very potent neuroleptics exhibiting a clear prolongation of the central depressant and some prolongation of the cataleptic activity.

Carbonyl halides of the Group VI transition metals. XI. Dithiocyanatocarbonyl derivatives of molybdenum and tungsten(II)

1968 ◽  
Vol 21 (6) ◽  
pp. 1435 ◽  
Author(s):  
R Colton ◽  
GR Scollary
Keyword(s):  
Transition Metal ◽  
Transition Metals ◽  
Ammonium Chloride ◽  
Pure State ◽  
Ammonium Thiocyanate ◽  
Donor Ligands ◽  
Group Vi ◽  
Derivatives Of ◽  
And Tungsten

Reaction of ammonium thiocyanate with dihalocarbonyls of molybdenum and tungsten(11) leads to the elimination of ammonium chloride and the formation of a dithiocyanatocarbonyl complex of the transition metal. Although the thiocyanatocarbonyls themselves have not been isolated in a pure state, a number of substituted derivatives with phosphorus donor ligands have been prepared and characterized. In general these complexes are less stable than the corresponding carbonyl halide derivatives.

Substitution Reactions and Meso Derivatives of 1,2-Benzanthracene

1938 ◽  
Vol 60 (8) ◽  
pp. 1893-1896 ◽  
Author(s):  
Louis F. Fieser ◽  
E. B. Hershberg
Keyword(s):  
Substitution Reactions ◽  
Derivatives Of

Organometalloidal derivatives of the transition metals

1992 ◽  
Vol 430 (3) ◽  
pp. 273-286 ◽  
Author(s):  
Antonio Guerrero ◽  
Jacobo Gómez-Lara ◽  
Jorge Cervantes ◽  
Luis Velasco ◽  
Hemant Sharma ◽  
...  
Keyword(s):  
Transition Metals ◽  
Derivatives Of
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