摘要:

The successful synthesis of sodium triphenylgermanethiol (1), (C6H5)3GeSNa, and disodium diphenylgermanedithiol, (C6H5)2Ge(SNa)2, have made it possible to carry out reactions with RX type compounds yielding a variety of organogermanium-sulphur compounds. In addition, triphenylgermanethiol, (C6H5)3GeSH, has been synthesized for the first time. Reactions of these compounds are related to analogous group IV element compounds. Physical and chemical properties of these new compounds are also discussed.

ISSN:0008-4042    

DOI:10.1139/v63-180

出版商:NRC Research Press    

年代:1963

数据来源: NRC

摘要:

The bonding in Mn(CO)5X complexes is described in terms of molecular orbitals. The axial CO group is assumed to be bonded much more strongly to Mn than the other four CO groups. The molecular orbital energy level scheme thus derived successfully accounts for the principal features of the electronic spectra of Mn(CO)5X complexes in different solvents. The first charge transfer band is assigned as ann(Mn) → π*(CO) type transition. Thisn → π* assignment is supported by the fact that the maximum of the band for Mn(CO)5Br is shifted to higher energies on increasing the polarity of the solvents employed.Kinetic studies of Mn(CO)5X-14CO exchange reveal that the axial CO is more inert than the other four CO groups; also, the rates of14CO exchange of the four equivalent CO groups in Mn(CO)5X complexes depend strikingly on the nature of the X−ligand. A consistent interpretation of the above results and the observed kinetics of some typical substitution reactions of Mn(CO)5X complexes is presented in terms of the derived electronic structural description.

ISSN:0008-4042    

DOI:10.1139/v63-181

出版商:NRC Research Press    

年代:1963

数据来源: NRC

摘要:

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.

ISSN:0008-4042    

DOI:10.1139/v63-182

出版商:NRC Research Press    

年代:1963

数据来源: NRC

摘要:

The orbital electronegativities of the neutral transition metals of the first transition series have been calculated by the Mulliken formula for a wide variety of hybrid states. The electron affinities needed in the process have been calculated by isoelectronic and isoconfigurational extrapolation.

ISSN:0008-4042    

DOI:10.1139/v63-183

出版商:NRC Research Press    

年代:1963

数据来源: NRC

摘要:

The reaction of methylmagnesium bromide with benzophenone in tetrahydrofuran was found to be homogeneous and essentially quantitative. The rates of this reaction were measured by following the decrease in absorbance of benzophenone in the ultraviolet as a function of time. Variables examined were concentrations of reactants, magnesium bromide, and temperature. Values were derived for the rate constants, and the energy and entropy of activation. The reaction was found to be initially first order in each reactant, but the rate decreased faster with time than would be predicted from the simple second-order rate equation. The implications of these findings are discussed.

ISSN:0008-4042    

DOI:10.1139/v63-184

出版商:NRC Research Press    

年代:1963

数据来源: NRC

摘要:

Some synthesis and exchange reactions of diborane and its alkyl derivatives and of the higher boron hydrides were reviewed as background for new work.In pursuit of an idea prompted by knowledge of the deuterium and B10exchanges found for the reactive and unstable higher boron hydrides B4H10and B5H11, mono- and di-methyldi-hydropentaborane and methyltetraborane have been prepared by direct reaction between the parent higher hydrides and 1,2-dimethyldiborane or monomethyldiborane. The identity and the reactions of each product have been delineated by gas chromatographic separation, gas density, and mass, infrared, and n.m.r. spectrometry. The H1n.m.r. spectrum of dihydro-pentaborane has been reinterpreted and used to decide that monomethyldihydropentaborane is probably a BIIIderivative which displays stereoisomerism.

ISSN:0008-4042    

DOI:10.1139/v63-185

出版商:NRC Research Press    

年代:1963

数据来源: NRC

摘要:

The reactions of Me3Al with Me2NNMe2and Me2NCH2NMe2have yielded complexes whose n.m.r. spectra suggest cyclic structures. They have the formulas Me3Al:Me2NNMe2and Me3Al:Me2NCH2NMe2respectively. Me3Al reacts with Me2NCH2CH2NMe2to form a complex with a linear structure and the formula Me3Al:Me2NCH2CH2NMe2:AlMe3.The reactions of H3Al:NMe3with several methyl hydrazines have yielded the following compounds: [—Al(HNNHMe)NHNMe—]n, [—HAlNNMe2—]n, H2Al—NHNEt2, [(—HAlNNEt2—):NMe3]n, and H2Al—NMe2. No reaction occurred between H3Al·(Et2O)nand tetramethylhydrazine and the reaction of 3 moles of H2NNMe2with 1 mole of H3Al:NMe3yielded a compound for which no structural formula could be assigned, but which had emperical formula C4H15N5Al.

ISSN:0008-4042    

DOI:10.1139/v63-186

出版商:NRC Research Press    

年代:1963

数据来源: NRC

摘要:

Reactions of diethylzinc with isopropanol and water were studied by means of infrared absorption and gas evolution. The former method was found to be more reliable. Ethylzinc isopropoxide, formed from diethylzinc and isopropanol, was shown to be stable in the presence of excess isopropanol. The reaction of diethylzinc with water was found to proceed in a two-step manner, the product of the first being ethylzinc hydroxide. The decomposition of ethylzinc hydroxide was found to be first order with respect to itself and independent of diethylzinc.

ISSN:0008-4042    

DOI:10.1139/v63-187

出版商:NRC Research Press    

年代:1963

数据来源: NRC