Reaction of diazonium salts with transition metals : IX. Reaction of vinyltrimethylsilane with arenediazonium tetrafluoroborates under palladium(0) catalysis

Arenediazonium tetrafluoroborates (ArN₂BF₄ where Ar=Ph, 4-MeC₆H₄, 4-BrC₆H₄, 4-IC₆H₄ and 4-NO₂C₆H₄) reacted easily with CH₂=CHSiMe₃ at 25 δC to give ArCH=CH₂, (E-ArCH=CHSiMe₃ and Ar(Me₃Si)C=CH₂ in excellent yields under palladium(O) catalysis. (E)-ArCH=CHSiMe₃ compounds were obtained predominantly and isolated in good yields by using an excess of CH₂=CHSiMe₃ over ArN₂BF₄. Protodesilylation of the reaction mixture afforded styrene derivatives.     

Reaction of diazonium salts with transition metals : X. Formylation of arenediazonium salts with carbon monoxide and silyl hydrides under palladium catalysis

Arenediazonium tetrafluoroborates (ArN₂BF₄ where Ar = X-C₆H₄; X = H, 2-Me, 3-Me, 4-Me, 4-MeO, 4-MeCO, 4-EtOCO, 2-Ph, 2-Cl, 3-Cl, 4-Cl, 4-Br, 4-I, 3-NO₂ and 4-NO₂) were easily converted to aromatic aldehydes (ArCHO) in good yields through the palladium-catalyzed reaction with CO and Et₃SiH or polymethylhydrosiloxane (PMHS) at room temperature.     

Reaction of diazonium salts with transition metals—III: Palladium(0)-catalyzed arylation of unsaturated compounds with arenediazoium salts

Palladium (0) catalyzed reactions of arenediazonium salts for arylation of aliphatic and cyclic olefins and allylic alcohols, styrene and ethyl acrylate were studied. Effects of the olefinic compounds and other reaction variables on the arylation were presented. Arylpalladium species was proposed as the most plausible intermediated in this reaction.     

Reaction of heterocyclic diazonium salts with hydrazones

Depending on the nature of the heteroring and the hydrazone, a formazan or a heterylazophenylhydrazone are formed in the reaction of an aryl hydrazone with the diazonium salt obtained from a heterocyclic amine. Disproportionate to form a triphenylformazan is also possible.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1062–1064, August, 1972     

Reaction of 5-alkylidenerhodanines with diazonium salts

In the action of diazonium salts on 5-alkylidenerhodanines, azo compounds are formed by the replacement of one or two hydrogen atoms in the methyl group. In the case of 5-ethylidenerhodanines, the formation of an azorhodanine through the replacement of the alkylidene residue by an arylazo group takes place simultaneously. In the formazyl derivatives the long-wave absorption maximum is displaced hypsochromically by 15–20 nm as compared with the dyes having a single azo group.     

Reaction of some organomercury compounds with diazonium salts

Summary We were the first to replace a mercury atom attached to a saturated carbon atom by the arylazo group. The reaction of the p-nitro- and 2,4-dinitrophenyldiazonium fluoborates with ethyl -bromomercuriphenylacetate and with bromomercurimethyl tert-butyl ketone give the corresponding arylhydrazones in good yields.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1711–1712, September, 1964     

Photochemical grafting of diazonium salts on metals

4-Nitrobenzenediazonium may be photochemically grafted onto gold, copper and iron under visible and UV light. Thin nanometre layers are obtained and characterized by IRRAS, electrochemistry and ellipsometry.     

Reaction of acetylenes with transition metals: VIII. π-allylpalladium complexes from acetylenes and alkenes

Coupling of diarylacetylenes with alkenes in the presence of dichlorobis(benzonitrile)palladium gives chloro(syn-1-chloro-anti-1-aryl-syn-3-alkyl)-π-allylpalladium complexes.     

Coordination compounds of hydrazine derivatives with transition metals. Part 22. Reaction of aroylhydrazones with copper(II) salts

Summary Two different crystalline forms namely the greenanti and the brownsyn were isolated from the reaction of copper(II) acetate with some aldehydic aroylhydrazones, while others gave only the brown form. With copper(II) chloride, however, reduction of copper(II) ions occurred and copper(I) chelates of general formula Cu(HL)Cl were obtained. Tridentate ligands such as salicylaldehyde and pyridine-2-carbaldehyde aroylhydrazones gave copper(II) chelates Cu(L)Cl₂. A tentative reduction mechanism involving intramolecular electron transfer was proposed. In such a mechanism the steric requirements of the aroylhydrazone molecule and the presence of a third coordination site would stabilize the dipositive oxidation state of copper.     

Biuret complexes of divalent transition metals.

The complexes M bi₂ X₂ with M = Mn, Co, Ni and Cu, X = Cl, Br and I have been prepared. IR spectra and magnetic properties are given. The analysis of the ligand field parameters obtained from the electronic spectra for the cobalt and nickel compounds are in agreement with a trans octahedral structure.     

Reaction of 2-dialkyl-5-formylfurans, -thiophenes,and-selenophenes with aromatic diazonium salts

The reaction of 2-dialkylamino-5-formylfurans, -thiophenes, and -selenophenes with diazonium salts gives azo dyes with elimination of the aldehyde group.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1325–1326, October, 1974.     

Cationic arylation through photo(sensitised) decomposition of diazonium salts. Chemoselectivity of triplet phenyl cations

The photodediazoniation of some 4-X-phenyldiazonium tetrafluoborates in MeCN leads to the singlet phenyl cations (X = H, tert-butyl, NMe2, CN), which add to the solvent yielding the corresponding acetanilides. Triplet sensitisation, however, leads to the triplet phenyl cation, which is reduced in neat solvent and is trapped by pi nucleophiles (allyltrimethylsilane and benzene), resulting in an ionic analogue of the Meerwein or Gomberg arylations. With the 4-nitro derivative intersystem crossing prevails over dediazoniation from the singlet and with the 4-cyano competes with it, so that in those cases the triplet phenyl cation is formed also upon direct irradiation.     

Reaction of aminoalcohols with butadiene catalyzed by palladium complexes. Preliminary communication

The aminoalcohols 1 , react with 2 equivalents of butadiene in the presence of catalytic quantities of bis (acetylacetonato)palladium/triphenylphosphine to give exclusively the corresponding N-octadienyl amninoalcohols. In the presence of excess butadiene, subsequent O-octadienylation occurs only for N-octadienylimino-diethanol 2g , affording the monoether 4g . O-octadienylation of 2a-f and 4g can be effected by the addition of molar quantities of triethylamine to the reaction mixture.     

Sterically hindered diazonium salts for the grafting of a monolayer on metals

An organic monolayer is obtained on Cu, Au, and SiH by electrografting 3,5-bis-tert-butyl benzenediazonium tetrafluoroborate, as evidenced by cyclic voltammetry, IR-ATR, and ellipsometry. This results from the bulky groups at the 3,5-positions that sterically hinder the growth of the layer.     

Nitrosophenol complexes of transition metal salts

Complexes derived from 4-substituted-2-nitrosophenols, 3-Me-2-nitrosophenol, nitrosophyrogallol, nitrososalicylic acid and nitrosogallic acid with cobalt(II), nickel(II) and copper(II) have been prepared and characterized by elemental analysis, electronic and vibrational spectra, together with magnetic susceptibility measurements. The e.s.r. spectra of the copper(II) complexes were investigated, and detailed thermal properties of selected complexes are discussed.     

Norbornadiene complexes of transition metals

Conclusions Correlations were established between the stereochemistry of 2-(-carbinol)norbornadiene complexes of rhodium and their mass spectra.This study is also communication 30 from the series Mass Spectrometry of Transition Metal- Complexes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2701–2703, December, 1982.