摘要:

AbstractSeveral complexes of general formula M(2MIz)n(anion)2, with M = Mn, Fe, Co, Ni, Cu, Zn and Cd are reported. The anions are ClO−4and BF−4, n = 4 or 6, and 2MIz stands for 2‐methylimidazole.The compounds are prepared from alcoholic solutions of the ligand and the metal salt in the presence of triethyl orthoformate.Structural conclusions are drawn from infrared spectra, ligand‐field spectra, X‐ray powder diagrams and paramagnetic resonance measurements.Depending upon the particular cation, the metal ions were found to be tetragonally (Mn, Fe, Cd), tetrahedrally (Co, Zn), square planar (Cu, Ni), or octahedrally (Cd) coordinated. In the tetragonal compounds the ClO−4and BF−4anions are very weakly coordinated to the metal ions. No anion coordination occurs in the remain

ISSN:0165-0513    

DOI:10.1002/recl.19720910502

出版商:WILEY‐VCH Verlag    

年代:1972

数据来源: WILEY

摘要:

AbstractThe isomer distributions and the partial rate factors for the nitration of eighttertiaryalkylbenzenes and fivetertiarycycloalkylbenzenes have been determined. Thefmvalues for thetertiaryalkylbenzenes are greater than for theprimaryandsecondarycompounds. Thefpvalue for (1‐methylcyclopropyl)‐benzene shows that the pseudo conjugation between the cyclopropyl group and the benzene ring is disturbed. The steric hindrance of the nitration in theortho‐positions increases greatly as the branching of the alkyl groups incr

ISSN:0165-0513    

DOI:10.1002/recl.19720910503

出版商:WILEY‐VCH Verlag    

年代:1972

数据来源: WILEY

摘要:

AbstractUV irradiation of 4‐(2,6‐diphenylphenoxy)‐2,6‐diphenylanisole (I, R=Ph) affords a single product resulting from cleavage of the central (aromatic) ether bond and subsequent rearrangement to a pendant (ortho) pheny

ISSN:0165-0513    

DOI:10.1002/recl.19720910504

出版商:WILEY‐VCH Verlag    

年代:1972

数据来源: WILEY

摘要:

AbstractCalculation methods for the evaluation of the parameters g, D and E for an S = 1 system, from paramagnetic resonance powder spectra are discussed and applied to a number of compounds having the general formula Ni(ligand)6(anion)2; in this formula the ligands are nitrogen donors such as nitriles, pyrazoles and imidazoles, with large anions like ClO−4, BF−4, SbCl−6, InBr−4and GaCl−4.A treatment similar to that of organic triplet molecules can be used for the interpretation, despite the fact that the observed bands are rather broad.In the present compounds the g‐values were found to be isotropic within experimental error in the region 2.17‐2.20; the D‐values varied from 0.05‐0.90 cm−1in the several compounds. The rhombic distortion (usually expressed as λ = E/D) was found to be small for most compounds, although λ‐values of 0.10, 0.16 a

ISSN:0165-0513    

DOI:10.1002/recl.19720910505

出版商:WILEY‐VCH Verlag    

年代:1972

数据来源: WILEY

摘要:

AbstractIn order to confirm the multiple ring structure of benzotris[c]‐2‐oxyfurazan (“hexanitrosobenzene”), the electron‐binding energies of carbon, nitrogen and oxygen in this compound have been measured by X‐ray photoelectron spectroscopy. Charge calculations have been carried out by various methods for the interpretation of the results.For each type of atom the 1s electron energy peak was split into two peaks of approximately equal intensity: carbon, 285.6 and 287.5 eV; nitrogen, 401.3 and 405.0 eV; oxygen, 533.4 and 535.0 eV. The carbon values may be less reliable because of deposition of pump oil onto the sample.These results exclude the hexanitroso structure and support the furazan structure for which further evidence has already bee

ISSN:0165-0513    

DOI:10.1002/recl.19720910506

出版商:WILEY‐VCH Verlag    

年代:1972

数据来源: WILEY

摘要:

Abstract1,3,5‐Trinitrobenzene takes up three methylene groups from diazomethane at −80° to give 1 (Scheme 1).Reduction of I with NaBH4in pyridine yields the dihydro derivative II by saturation of the nitro‐olefinic double bond in I.In a protic solvent like methanol, this reaction proceeds with rupture of the isoxazoline‐N‐oxide ring, and leads to the intermediary formation of a nitroso‐and a primary alcohol‐function. The nitroso‐group reacts spontaneously further with a nearby HCNO2‐fragment, and this transannular process generates the tropane ring‐system of III. The hydroxyl‐group at the nitrogen‐bridge is easily oxidised, to give a relatively stable nitroxide, detectable by ESR. Spectral data, including X‐ray analysis of III1fully confi

ISSN:0165-0513    

DOI:10.1002/recl.19720910507

出版商:WILEY‐VCH Verlag    

年代:1972

数据来源: WILEY

摘要:

AbstractA mechanistic and kinetic study has been made of thecis/trans‐isomerisation ofcis‐azodioxycyclohexane andcis‐azodioxymethane in acetonitrile at temperatures, varying from 0‐60°. Cross‐over and trapping experiments show that the isomerisation does not proceed by rotation around the NN bond but exclusivelyviadissociation and recombination of free monomer molecules. Kinetic data indicate that the monomer molecules dimerize at low temperature by kinetic control chiefly to thecis‐isomer. At elevated temperatures the thermo‐dynamically more stabletrans‐isomer is formed. Activation parameters show that the formation of thecis‐isomer from two monomer molecules is controlled by entropy rather than

ISSN:0165-0513    

DOI:10.1002/recl.19720910508

出版商:WILEY‐VCH Verlag    

年代:1972

数据来源: WILEY

摘要:

Abstract1‐Alkynyl allenyl sulfides H2C=C=CHSC≡ CR1(R1= CH3, C2H5), prepared from alkynethiolates LiSC≡CR1and propargyl bromide in liquid ammonia, rearrange at room temperature to thioketenes HC≡CCH2C(R1)=C=S. These can be trapped by amines R22NH (R2= C2H5, C3H7) to give the acetylenic thioamides H≡CCH2CH(R1)C(=S)NR22in fair to good yields. Potassiumtert‐butoxide in liquid ammonia causes cyclization of the thioamides to 2‐dialkylamino‐3,5‐dialkylthiophenes. The same thiophenes are obtained by simply heating the thioamides

ISSN:0165-0513    

DOI:10.1002/recl.19720910509

出版商:WILEY‐VCH Verlag    

年代:1972

数据来源: WILEY

摘要:

AbstractThe isomer distribution in the sulfonation of toluene with 95.8% H2SO4at 25° in the presence of some sulfonic acids and other addenda was determined. All the addenda studied effect a decrease in the degree ofortho‐substitution. Most effective arep‐t‐butylbenzenesulfonic acid, methyl trimethylphenylammonium sulfate and nitrobenzene. The effect of methanesulfonic acid is very small, that of water and of sodium bisulfate almost negligible. The degree ofmeta‐substitution is small and is unaffected by the addenda.The variations in the isomer distribution are discussed in terms of changes in the solvation of the reactants and of the transitio

ISSN:0165-0513    

DOI:10.1002/recl.19720910510

出版商:WILEY‐VCH Verlag    

年代:1972

数据来源: WILEY

摘要:

AbstractThe preparation of tricyclohexylphosphine complexes of osmium and ruthenium is reported. The reaction of K2OsCl6or hydrated RuCl3with tricyclohexylphosphine (PCy3) in 2‐methoxyethanol leads to the complexes MHCl(CO) (PCy3)2with M = Os or Ru. Hydrogen‐deuterium exchange of PCy3was observed in these complexes on reaction with deuterium gas and in the complexes prepared with deuteriated ethanol. Addition of pyridine (py) gives complexes of the formula MHCl(CO) (PCy3)2(py). Phosphonium compounds containing iron(III) and osmium(IV) halides as anions were prepared and characteri

ISSN:0165-0513    

DOI:10.1002/recl.19720910511

出版商:WILEY‐VCH Verlag    

年代:1972

数据来源: WILEY