摘要:

Several isotopically substituted triphenylphosphine stabilized dimethyl platinum compounds of the type (Ph3P)2PtMe2where Me = CH3, CH2D, CD2H, and CD3have been prepared and their infrared spectra in the CH and CD Stretching regions have been examined. The assignments of the stretching vibrations of the methyl group have been confirmed by means of an application of the Average Rule for isotopically substituted species. The possible application of the Average Rule as a general method for assigning CH stretching modes is discussed and it is suggested that the method could be used to confirm some recently proposed reassignments of the traditional Fox and Martin assignments. The method may also be used by surface chemists as a means of determining the number of hydrogen atoms in an adsorbed XHnspecies.

ISSN:0008-4042    

DOI:10.1139/v71-488

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

The preparation of complexes with the empirical formula WCl5L (L = Ph3PS, Ph3PSe) and WBr4•-Ph3PS is reported. The tungsten chloride adducts have been formulated as [W2Cl8L2]2Cl on the basis of infrared spectra, molecular weight, and conductance measurements. The complex WBr4Ph3PS is probably a non-ionic dimer, but solubility problems make this suggestion tentative. No corresponding complex with Ph3PSe could be isolated.The shifts in v(P—X) (X = S, Se) upon coordination are amongst the largest ever reported, and are indicative of bridging behavior by these ligands.

ISSN:0008-4042    

DOI:10.1139/v71-489

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

The infrared and Raman spectra of the series of iodo(methyl)germanes, CH3GeI3, (CH3)2GeI2, and (CH3)3GeI have been recorded. A normal coordinate analysis based on a modified valence force field confirms thea prioriassignments for all of the fundamental frequencies except the torsional modes.

ISSN:0008-4042    

DOI:10.1139/v71-490

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

19F nuclear magnetic resonance (n.m.r.) studies show that SbF5forms HSbF5(OOCCF3) in tri-fluoroacetic acid. This complex acid does not react with (CF3CO)2O which must be added to carry out conductimetric studies in anhydrous HOOCCF3. However, HClO4, HSO3F, and HNO3all react with (CF3CO)2O to yield mixed anhydrides CF3COClO4, CF3COSO3F, and NO2OOCCF3. HBF4reacts with the anhydride to give CF3COF while H2SO4appears to be simply dehydrated to polysulfuric acids.

ISSN:0008-4042    

DOI:10.1139/v71-491

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

Osmometric measurements have been made on the alkali metal persulfates, and these are interpreted in terms of formation of ion pairs, MS2O8−, by means of the method of Masterton and Berka (5). Equilibrium constants, and the derived thermodynamic quantities are deduced for the reactions. These results are applied to the interpretation of the kinetics of the reactionsWith M = K+, Rb+, and Cs+, the reacting species are MFe(CN)63− + MS2O8−, with very similar rate constants; with M = Li+, Na+the species are MFe(CN)63− + S2O82−; and for lithium the reaction of Fe(CN)64− + S2O82−is also important. Rate constants and activation parameters are deduced.

ISSN:0008-4042    

DOI:10.1139/v71-492

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

[SCH3Fe(CO)3]2when separated into its two known isomers reacts with tertiary phosphines with retention of the sulfur-methyl group configuration. The reaction of the mixture of isomers of [SCH3-Fe(CO)3]2with ditertiary phosphines and arsines has been studied. Some ligands give bridged complexes and others chelates: one ligand gives both. The p.m.r. and Mössbauer spectra of these complexes are discussed.

ISSN:0008-4042    

DOI:10.1139/v71-493

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

Solid Perfluoromethlycyclohexane has been studied by X-ray diffraction, n.m.r., and e.s.r. The two former methods confirm the existence of several thermodynamically stable crystalline phases between 77 °k and the melting point (234 °K): phase I (227 < T < 234 °K), phase II (173 < T < 227 °K), phased III (T < 173 °K) and that of a metastable phase (II′) below 130 °K. When the temperature is raised, the n.m.r., indicates successively the rotation of CF3(phases II′ and III), the reorientation (phase I). Similar information is obtained from e.s.r. concerning the motions ofradicals trapped in PFMCH.The comparison betweenganisotropy, measured from the position of the peaks of e.s.r. spectra and that deduced from their second moments suggests a wide distribution of reorientaion correlation times for radicals in the metastable phase.

ISSN:0008-4042    

DOI:10.1139/v71-494

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

Strong mineral acids convert 1,1,1-trichloro-2-hydroxy-4-alkanones to 1,1,1-trichloro-2-aIken-4-ones and 1,1,5-trichloro-1-alken-4-ones via an intramolecular chlorine shift from C-1 to −5 of an enol allylic system. Alternatively, 1,1,1-trichloro-2-alken-4-ones may be synthesized from 1,1,1-trichloro-2-hydroxy-4-alkanones by acetylation and elimination of acetic acid or by nucleophilic substitution with thionyl chloride followed by dehydrohalogenation. The two diastereomeric 1,1,1-trichloro-2-hydroxy-3-methyl-4-hexanones do not epimerize during acetylation, and theerythro-acetate resists elimination of acetic acid. Pyrolysis of 2-(1-hydroxy-2,2,2-trichloroethyl-)cyclohexanone yields 2-(2,2-dichlorovinyl)-2-cyclohexenone while treatment of 1,1,1,7,7,7-hexachloro-2,6-dihydroxy-4-heptanone with strong acid leads to the formation of 1,1,1,7,7,7-hexachloro-2,5-heptadien-4-one.

ISSN:0008-4042    

DOI:10.1139/v71-495

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

In neutron-irradiated [CpFe(CO)2]2radioactive FeCp2and Fe(CO)5are formed, in addition to the radioactive parent compound. The radiochemical yields before annealing are 1.4, 3.2, and 16.0%, respectively. The predominance of Fe(CO)5over FeCp2is in keeping with previous observations. The yield of radioferrocene is not affected by subsequent thermal treatment at up to 75°, while the yields of the two carbonyl-containing compounds are increased up to 5.4 and 20.1%. The ferrocene yield is insensitive to irradiation time and temperature. From this insensitivity it is concluded that the Fe—Cp bonds are reformed by epithermal processes. Similarly the Fe—CO bonds are reformed by thermal as well as epithermal reactions.

ISSN:0008-4042    

DOI:10.1139/v71-496

出版商:NRC Research Press    

年代:1971

数据来源: NRC

摘要:

The preparation of ((CH3)2CHS)2AlCH3and (t-CaH9S)2AlCH3is reported. The reactions of (RS)2AlCH3(R = CH3, (CH3)2CH,t-C4H9) with ketones give aldol condensations leading to the corresponding conjugated ketones, with the acetyl group R—CO—CH3; with other ketones, a mixture of thioacetal and enolthioether is obtained. With aldehydes, a mixture of thioacetal and enolthioether is observed. With olefins there is an addition of two RS groups on the site of the double bond, with a small percentage of allylic substitution. With conjugated ketone, the saturated ketone is obtained with the alkylthio group in β position. All those reactions proceed with good yields and appear quite general.

ISSN:0008-4042    

DOI:10.1139/v71-497

出版商:NRC Research Press    

年代:1971

数据来源: NRC