13 C Chemical shifts, when corrected for the diamagnetic term, become additive for polysubstitution by halogen, or methyl, methoxy-, or phenyl groups; and the branched alkanes, and fused (or linked) arenes, follow the simple rules. The corrected shifts for acyclic (including branched) alkanes and simple cycloalkanes (except cyclopropane) are given by five parameters which are increments for each α-, β-, γ-, and δ-carbon substituent, and a small constant term to include methane. The methylcyclohexane parameters vary with conformation.The increase in corrected (paramagnetic) shift with substitution is related to the molecular orbital theory. The shift increases as QAB, the double bond term, increases.The corrected shift has a periodic relationship with the atomic number of the ligand X in MenX. The corrected shift increases across the period of the ligand X (as its electronegativity increases), but also increases down the group of the ligand (as its electronegativity decreases), except for a small decrease from the first row to the second for the more electronegative ligands.While increments in corrected shift are additive for saturated ligands, conjugative interaction with multiply bonded substituents reduces the resultant paramagnetic shift.
{"title":"The interpretation of carbon nuclear magnetic resonance shifts","authors":"J. Mason","doi":"10.1039/J19710001038","DOIUrl":"https://doi.org/10.1039/J19710001038","url":null,"abstract":"13 \u0000 C Chemical shifts, when corrected for the diamagnetic term, become additive for polysubstitution by halogen, or methyl, methoxy-, or phenyl groups; and the branched alkanes, and fused (or linked) arenes, follow the simple rules. The corrected shifts for acyclic (including branched) alkanes and simple cycloalkanes (except cyclopropane) are given by five parameters which are increments for each α-, β-, γ-, and δ-carbon substituent, and a small constant term to include methane. The methylcyclohexane parameters vary with conformation.The increase in corrected (paramagnetic) shift with substitution is related to the molecular orbital theory. The shift increases as QAB, the double bond term, increases.The corrected shift has a periodic relationship with the atomic number of the ligand X in MenX. The corrected shift increases across the period of the ligand X (as its electronegativity increases), but also increases down the group of the ligand (as its electronegativity decreases), except for a small decrease from the first row to the second for the more electronegative ligands.While increments in corrected shift are additive for saturated ligands, conjugative interaction with multiply bonded substituents reduces the resultant paramagnetic shift.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1977-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89384191","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The various theories of optical activity are applied to the differential Raman scattering of circularly polarized light by optically active molecules. In particular, the ‘one electron’ theory provides simple symmetry rules which enable the dissymmetric environments of functional groups with well-defined ‘fingerprints’ in the Raman spectrum to be probed, and this could yield more detailed conformational and structural information than the o.r.d. and c.d. bands of dissymmetrically perturbed chromophores.
{"title":"Symmetry rules for the differential Raman scattering of circularly polarized light by optically active molecules","authors":"L. Barron","doi":"10.1039/J19710002899","DOIUrl":"https://doi.org/10.1039/J19710002899","url":null,"abstract":"The various theories of optical activity are applied to the differential Raman scattering of circularly polarized light by optically active molecules. In particular, the ‘one electron’ theory provides simple symmetry rules which enable the dissymmetric environments of functional groups with well-defined ‘fingerprints’ in the Raman spectrum to be probed, and this could yield more detailed conformational and structural information than the o.r.d. and c.d. bands of dissymmetrically perturbed chromophores.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73541844","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The spectroscopic properties of the complexes [FeIII(edtaH)(H2O)], [FeIII(edta)(H2O)]– and [FeIII(hedta)(H2O)2](edta = ethylenediamine tetra-acetate and hedta = hydroxyethylethylenediamine triacetate) have been examined in various solvents and in the solid state. By correlating the known structures of the EDTA complexes with their characteristically different absorption spectra in the solid state, it is possible to indicate the co-ordination in various solvents. All complexes have been found to be seven-co-ordinate in water, methanol, formamide, and glycerol but six-co-ordinate in dimethylformamide (DMF) and dimethyl sulphoxide (DMSO). The results suggest that in solution the complexes contain pentadentate edta or hedta and either two or one co-ordinated solvent molecules the number of which is determined by the steric requirements of the solvent molecule. The Mossbauer parameters of the complexes are discussed.
{"title":"Variable co-ordination of iron(III) complexes in co-ordinating solvents","authors":"K. Garbett, G. Lang, R. J. Williams","doi":"10.1039/J19710003433","DOIUrl":"https://doi.org/10.1039/J19710003433","url":null,"abstract":"The spectroscopic properties of the complexes [FeIII(edtaH)(H2O)], [FeIII(edta)(H2O)]– and [FeIII(hedta)(H2O)2](edta = ethylenediamine tetra-acetate and hedta = hydroxyethylethylenediamine triacetate) have been examined in various solvents and in the solid state. By correlating the known structures of the EDTA complexes with their characteristically different absorption spectra in the solid state, it is possible to indicate the co-ordination in various solvents. All complexes have been found to be seven-co-ordinate in water, methanol, formamide, and glycerol but six-co-ordinate in dimethylformamide (DMF) and dimethyl sulphoxide (DMSO). The results suggest that in solution the complexes contain pentadentate edta or hedta and either two or one co-ordinated solvent molecules the number of which is determined by the steric requirements of the solvent molecule. The Mossbauer parameters of the complexes are discussed.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73887111","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The catalysis of cyclopentane–deuterium exchange by nickel–copper alloy films persists to low (4 atom %) nickel content. Activation energies where measurable and product distribution patterns are constant for nickel contents greater than ca. 24 atom % nickel, but below this value there is a marked increase in over-all activation energy and an even-numbered distribution pattern (maxima for tetra- and hexa-deuterio-products) develops. The latter feature is ascribed to doubly bonded intermediate described as ααββ- and ααββγγ-adsorbed. These are the species believed to be responsible for the severe self-poisoning found on pure nickel. The strength of their adsorption decreases with the increasing fraction of copper, causing initially a decrease in the extent of self-poisoning and ultimately the appearance of the even-numbered deuteriocyclopentane exchange products. These features are discussed in terms of compositional and texture changes.
{"title":"Exchange reaction between cyclopentane and deuterium on evaporated nickel–copper alloy films","authors":"E. Mcmahon, P. F. Carr, J. Clarke","doi":"10.1039/J19710002012","DOIUrl":"https://doi.org/10.1039/J19710002012","url":null,"abstract":"The catalysis of cyclopentane–deuterium exchange by nickel–copper alloy films persists to low (4 atom %) nickel content. Activation energies where measurable and product distribution patterns are constant for nickel contents greater than ca. 24 atom % nickel, but below this value there is a marked increase in over-all activation energy and an even-numbered distribution pattern (maxima for tetra- and hexa-deuterio-products) develops. The latter feature is ascribed to doubly bonded intermediate described as ααββ- and ααββγγ-adsorbed. These are the species believed to be responsible for the severe self-poisoning found on pure nickel. The strength of their adsorption decreases with the increasing fraction of copper, causing initially a decrease in the extent of self-poisoning and ultimately the appearance of the even-numbered deuteriocyclopentane exchange products. These features are discussed in terms of compositional and texture changes.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75744444","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The splitting and the order of 3d- and 4d-orbital energies for some complexes of the first- and second-transition series having dodecahedral geometry is calculated by the simple crystal-field model. The relative order of energy levels depends on the nature of the ligands and their distances from the metal. The energy behaviour is further examined as a function of the ratio G2 : G4 by assuming first all ligands equal and at the same distance from central metal, and then for cases when all ligands are equal but at different distances from the central metal. The discussion is extended to cases when different ligands are present in the complex. The results suggest that there is no representative energy diagram valid for all MX8 dodecahedral complexes. The calculations are applied to some complexes of Zr, Mo, Ti, Cr, and Co in order to illustrate the variations met in actual cases. It is found that dxy is the most stable for 4d and dz2 for 3d complexes examined.
{"title":"Ligand-field splitting in eight-co-ordinate complexes of dodecahedral structure","authors":"M. Randic, M. Vučelić","doi":"10.1039/J19710003309","DOIUrl":"https://doi.org/10.1039/J19710003309","url":null,"abstract":"The splitting and the order of 3d- and 4d-orbital energies for some complexes of the first- and second-transition series having dodecahedral geometry is calculated by the simple crystal-field model. The relative order of energy levels depends on the nature of the ligands and their distances from the metal. The energy behaviour is further examined as a function of the ratio G2 : G4 by assuming first all ligands equal and at the same distance from central metal, and then for cases when all ligands are equal but at different distances from the central metal. The discussion is extended to cases when different ligands are present in the complex. The results suggest that there is no representative energy diagram valid for all MX8 dodecahedral complexes. The calculations are applied to some complexes of Zr, Mo, Ti, Cr, and Co in order to illustrate the variations met in actual cases. It is found that dxy is the most stable for 4d and dz2 for 3d complexes examined.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73071916","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Complexes of the type Ni(aniline)n(NCS)2(n= 2, 4, and 6) are reported for a wide range of substituted anilines. The stable green 2 : 1 complexes have polymeric six-co-ordinate structures, and sulphur co-ordination by bridging thiocyanate produces splitting of the first and second electronic absorption bands, enabling estimates of the planar and axial ligand fields to be made. The NCS bending frequencies for bridging thiocyanate occur as a doublet in the range 450–490 cm–1. With ortho-substituted anilines, only, blue complexes of the type Ni(amine)4(NCS)2, have also been obtained, with N-bonded anion. For para-substituted anilines only blue 6 : 1 complexes have also been isolated, and ionic structures of the type [Ni(amine)6](NCS)2 are suggested, rather than formulation as [Ni(amine)4(NCS)2](amine)2, with lattice aniline.
{"title":"Arylamine co-ordination complexes. Part IV. Complexes of nickel(II) thiocyanate with substituted anilines","authors":"A. Butcher, D. J. Phillips, J. Redfern","doi":"10.1039/J19710001640","DOIUrl":"https://doi.org/10.1039/J19710001640","url":null,"abstract":"Complexes of the type Ni(aniline)n(NCS)2(n= 2, 4, and 6) are reported for a wide range of substituted anilines. The stable green 2 : 1 complexes have polymeric six-co-ordinate structures, and sulphur co-ordination by bridging thiocyanate produces splitting of the first and second electronic absorption bands, enabling estimates of the planar and axial ligand fields to be made. The NCS bending frequencies for bridging thiocyanate occur as a doublet in the range 450–490 cm–1. With ortho-substituted anilines, only, blue complexes of the type Ni(amine)4(NCS)2, have also been obtained, with N-bonded anion. For para-substituted anilines only blue 6 : 1 complexes have also been isolated, and ionic structures of the type [Ni(amine)6](NCS)2 are suggested, rather than formulation as [Ni(amine)4(NCS)2](amine)2, with lattice aniline.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75493521","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The structure of primary nickel dithizonate Ni(Hdz)2 was determined from three-dimensional single-crystal X-ray data, collected by standard film techniques, and refined by the least-squares method to R= 0·12 for 2580 observed and unobserved reflections. The crystals are triclinic, space group P with a= 4·62, b= 10·99, c= 12·50 ± 0·02 A, α= 88·8, β= 97·4, γ= 99·1 ± 0·1°, and Z= 1. The molecule is centrosymmetric with the nickel atom in a square-planar environment bonded to each dithizone ligand through one nitrogen and one sulphur atom to give a five-membered chelate ring with Ni–S 2·19 and Ni–N 1·87 A. The unique non-phenyl hydrogen atom was located.
{"title":"Crystal and molecular structure of primary nickel dithizonate","authors":"M. Laing, P. Sommerville, P. Alsop","doi":"10.1039/J19710001247","DOIUrl":"https://doi.org/10.1039/J19710001247","url":null,"abstract":"The structure of primary nickel dithizonate Ni(Hdz)2 was determined from three-dimensional single-crystal X-ray data, collected by standard film techniques, and refined by the least-squares method to R= 0·12 for 2580 observed and unobserved reflections. The crystals are triclinic, space group P with a= 4·62, b= 10·99, c= 12·50 ± 0·02 A, α= 88·8, β= 97·4, γ= 99·1 ± 0·1°, and Z= 1. The molecule is centrosymmetric with the nickel atom in a square-planar environment bonded to each dithizone ligand through one nitrogen and one sulphur atom to give a five-membered chelate ring with Ni–S 2·19 and Ni–N 1·87 A. The unique non-phenyl hydrogen atom was located.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75540571","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The preparation of a representative series of lead thiolates, Pb(SR)2(R = Et, Bun, But, Ph, p-C6H4Me, o-C6H4Me, p-C6H4Cl), is reported. Thermal decomposition of these thiolates leads to the formation of lead sulphide and the organic sulphide, R2S. Reaction of the thiolates with sulphur (or selenium) gives lead sulphide (or selenide) and the organic disulphide, R2S2. An assessment of the stability of lead thiolates in common organic solvents is given.
报道了具有代表性的硫代酸铅系列Pb(SR)2(R = Et, Bun, But, Ph, p-C6H4Me, o-C6H4Me, p-C6H4Cl)的制备。这些硫酸盐的热分解导致硫化铅和有机硫化物R2S的形成。硫酸盐与硫(或硒)反应生成硫化铅(或硒化物)和有机二硫化物R2S2。对硫代酸铅在常见有机溶剂中的稳定性进行了评价。
{"title":"Preparation and some properties of lead thiolates","authors":"R. Shaw, M. Woods","doi":"10.1039/J19710001569","DOIUrl":"https://doi.org/10.1039/J19710001569","url":null,"abstract":"The preparation of a representative series of lead thiolates, Pb(SR)2(R = Et, Bun, But, Ph, p-C6H4Me, o-C6H4Me, p-C6H4Cl), is reported. Thermal decomposition of these thiolates leads to the formation of lead sulphide and the organic sulphide, R2S. Reaction of the thiolates with sulphur (or selenium) gives lead sulphide (or selenide) and the organic disulphide, R2S2. An assessment of the stability of lead thiolates in common organic solvents is given.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74103320","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The molecular geometries of π-cyclopentadienyl-trans-dicarbonyliodo(triphenylphosphine)molybdenum, (π-C5H5)-Mo(CO)2(PPh3)I, (I), and π-cyclopentadienyl-cis-carbonylchloro[1,2-bis(diphenylphosphino)ethane]molybdenum,(π-C5H5)Mo(CO)(PPh2CH2CH2PPh2)Cl, (II), have been determined by X-ray crystal-structure analysis. The compound (I) crystallizes in the triclinic space group P, with a= 9·475 ± 0·007, b= 10·667 ± 0·008, c= 12·370 ± 0·009 A, α= 90° 52′± 4′, β= 93° 57′± 3′, γ= 113° 2′± 3′, and Z= 2. The compound (II) crystallizes in the orthorhombic space group Pbca, with a= 17·421 ± 0·009, b= 23·764 ± 0·014, c= 13·783 ± 0·010 A, and Z= 8. The three-dimensional X-ray intensity data were collected on an automatic four-circle diffractometer with Mo-Kα radiation, and the atomic co-ordinates were deduced by Fourier and least-squares methods. The final values of the discrepancy index R are 7·5% over 3425 independent reflections for (I) and 6·7% over 1706 independent reflections for (II). Each molybdenum atom, formally seven-co-ordinate, is in a distorted square pyramid defined by the π-cyclopentadienyl ring at the apex and the other ligands at the corners of the base. The Mo–C(carbonyl) bond lengths are 1·984 ± 0·015 and 1·982 ± 0·018 A in (I) and 1·938 ± 0·018 A in (II), and the Mo–P bond lengths are 2·481 ± 0·005 A in (I) and 2·496 ± 0·004 and 2·439 ± 0·005 A in (II). The Mo–I and Mo–Cl distances are 2·858 ± 0·003 and 2·541 ± 0·005 A, and the difference between these (0·32 A) is close to the difference of 0·34 A between the covalent radii of chlorine and iodine atoms. The Mo–C-(cyclopentadienyl) separations in (I) range from 2·297 to 2·367, mean 2·333 A, while those in (II) range from 2·233 to 2·381, mean 2·310 A.
{"title":"Metal–carbonyl and metal–nitrosyl complexes. Part XI. Crystal and molecular structures of π-cyclopentadienyl-trans-dicarbonyliodo(triphenylphosphine)molybdenum and π-cyclopentadienyl-cis-carbonyl-chloro-[1,2-bis(diphenylphosphino)ethane]molybdenum","authors":"M. Bush, A. Hardy, Lj. Manojlović-Muir, G. A. Sim","doi":"10.1039/J19710001003","DOIUrl":"https://doi.org/10.1039/J19710001003","url":null,"abstract":"The molecular geometries of π-cyclopentadienyl-trans-dicarbonyliodo(triphenylphosphine)molybdenum, (π-C5H5)-Mo(CO)2(PPh3)I, (I), and π-cyclopentadienyl-cis-carbonylchloro[1,2-bis(diphenylphosphino)ethane]molybdenum,(π-C5H5)Mo(CO)(PPh2CH2CH2PPh2)Cl, (II), have been determined by X-ray crystal-structure analysis. The compound (I) crystallizes in the triclinic space group P, with a= 9·475 ± 0·007, b= 10·667 ± 0·008, c= 12·370 ± 0·009 A, α= 90° 52′± 4′, β= 93° 57′± 3′, γ= 113° 2′± 3′, and Z= 2. The compound (II) crystallizes in the orthorhombic space group Pbca, with a= 17·421 ± 0·009, b= 23·764 ± 0·014, c= 13·783 ± 0·010 A, and Z= 8. The three-dimensional X-ray intensity data were collected on an automatic four-circle diffractometer with Mo-Kα radiation, and the atomic co-ordinates were deduced by Fourier and least-squares methods. The final values of the discrepancy index R are 7·5% over 3425 independent reflections for (I) and 6·7% over 1706 independent reflections for (II). Each molybdenum atom, formally seven-co-ordinate, is in a distorted square pyramid defined by the π-cyclopentadienyl ring at the apex and the other ligands at the corners of the base. The Mo–C(carbonyl) bond lengths are 1·984 ± 0·015 and 1·982 ± 0·018 A in (I) and 1·938 ± 0·018 A in (II), and the Mo–P bond lengths are 2·481 ± 0·005 A in (I) and 2·496 ± 0·004 and 2·439 ± 0·005 A in (II). The Mo–I and Mo–Cl distances are 2·858 ± 0·003 and 2·541 ± 0·005 A, and the difference between these (0·32 A) is close to the difference of 0·34 A between the covalent radii of chlorine and iodine atoms. The Mo–C-(cyclopentadienyl) separations in (I) range from 2·297 to 2·367, mean 2·333 A, while those in (II) range from 2·233 to 2·381, mean 2·310 A.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74109859","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The mass spectra of a series of 1,3,5-trialkylborazines, B3H3N3R3(R = Et, Prn, Pri, Bun, Bu8, Bui, But) are reported and discussed. The dominant feature of the spectra is a group of ions which arise through cleavage of an alkyl radical from the α-carbon atom of an N-substituent in the molecular ion. These fragment species are isoelectronic with the benzyl or tropylium ions observed in the mass spectra of alkyl benzenes. Further fragmentation paths are described and are supported in the case of 1,3,5-triethylborazine by studies on deuteriated derivatives.
报道并讨论了一系列1,3,5-三烷基硼嗪B3H3N3R3(R = Et, Prn, Pri, Bun, Bu8, Bui, But)的质谱。光谱的主要特征是由分子离子中n取代基的α-碳原子裂解烷基自由基而产生的一群离子。这些片段与烷基苯的质谱中观察到的苯或tropyum离子是等电子的。对1,3,5-三乙基硼嗪的进一步裂解路径进行了描述，并通过对氘化衍生物的研究得到了支持。
{"title":"Borazines. Part V. The mass spectra of some 1,3,5-trialkylborazines","authors":"P. Powell, P. Sherwood, M. Stephens, E. Brittain","doi":"10.1039/J19710002951","DOIUrl":"https://doi.org/10.1039/J19710002951","url":null,"abstract":"The mass spectra of a series of 1,3,5-trialkylborazines, B3H3N3R3(R = Et, Prn, Pri, Bun, Bu8, Bui, But) are reported and discussed. The dominant feature of the spectra is a group of ions which arise through cleavage of an alkyl radical from the α-carbon atom of an N-substituent in the molecular ion. These fragment species are isoelectronic with the benzyl or tropylium ions observed in the mass spectra of alkyl benzenes. Further fragmentation paths are described and are supported in the case of 1,3,5-triethylborazine by studies on deuteriated derivatives.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78109997","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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