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Magnetic anisotropy and polarized electronic spectrum of dichlorotetrakis(thiourea)nickel(II) 二氯四(硫脲)镍(II)的磁各向异性和极化电子能谱
Journal of The Chemical Society A: Inorganic, Physical, Theoretical Pub Date : 1971-01-01 DOI: 10.1039/J19710002434
M. Gerloch, J. Lewis, W. R. Smail
{"title":"Magnetic anisotropy and polarized electronic spectrum of dichlorotetrakis(thiourea)nickel(II)","authors":"M. Gerloch, J. Lewis, W. R. Smail","doi":"10.1039/J19710002434","DOIUrl":"https://doi.org/10.1039/J19710002434","url":null,"abstract":"The magnetic anistropies and powder susceptibilities of Ni(thiourea)4Cl2 are reported in the temperature range 80–300 K, together with single-crystal polarized electronic spectra at room- and liquid-helium-temperatures. The results are interpreted within a C4v crystal-field model including spin–orbit coupling.Estimates of the crystal-field radial parameters Dq, Dt, and Ds are made by fitting the magnetic and spectral results, as are values for the spin–orbit coupling and orbital reduction factors.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":"1 1","pages":"2434-2440"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90322827","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}
引用次数: 5
Photochemical isomerizations and related reactions of some tertiary phosphine- and tertiary arsine-iridium(III) complexes 某些膦叔和砷叔铱(III)配合物的光化学异构化及相关反应
Journal of The Chemical Society A: Inorganic, Physical, Theoretical Pub Date : 1971-01-01 DOI: 10.1039/J19710003756
P. Brookes, C. Masters, B. Shaw
{"title":"Photochemical isomerizations and related reactions of some tertiary phosphine- and tertiary arsine-iridium(III) complexes","authors":"P. Brookes, C. Masters, B. Shaw","doi":"10.1039/J19710003756","DOIUrl":"https://doi.org/10.1039/J19710003756","url":null,"abstract":"The photochemical isomerization of complexes of the types mer-[IrX3L3], [IrHX2L3], and [IrX3(CO)L2](X = Cl, Br, or I; L = tertiary phosphine) are reported. Complexes of the type fac-[IrX3(PEt3)3](X = CNO, SCN, or N3) have been made from mer-[IrCl3(PEt3)3] by a light-induced reaction. The complexes mer-[IrCl3L3](L = PEt3, PBun3, or AsMe2Ph) react with PMe2Ph in light to give [IrCl3L2(PMe2Ph)]. Some reactions of complexes of the type fac-[IrX3L3] are described.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":"124 1","pages":"3756-3760"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90390729","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}
引用次数: 14
Photoionization of potassium hexacyanoferrate(II) 六氰高铁酸钾的光电离(II)
Journal of The Chemical Society A: Inorganic, Physical, Theoretical Pub Date : 1971-01-01 DOI: 10.1039/J19710001960
R. Ballard, G. A. Griffiths
{"title":"Photoionization of potassium hexacyanoferrate(II)","authors":"R. Ballard, G. A. Griffiths","doi":"10.1039/J19710001960","DOIUrl":"https://doi.org/10.1039/J19710001960","url":null,"abstract":"The photoionisation near threshold of both solid potassium hexacyanoferrate(II) and its solution in glycerol have been studied by a Millikan condenser method. Threshold photoionization energies and the photoelectric emission spectrum have been measured.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":"46 41 1","pages":"1960-1963"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76600392","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}
引用次数: 3
H–F Coupling constants and hindered internal rotation in NN-dimethyltrifluoroacetamide n -二甲基三氟乙酰胺中H-F偶联常数和受阻内旋
Journal of The Chemical Society A: Inorganic, Physical, Theoretical Pub Date : 1971-01-01 DOI: 10.1039/J19710001586
S. Ng
{"title":"H–F Coupling constants and hindered internal rotation in NN-dimethyltrifluoroacetamide","authors":"S. Ng","doi":"10.1039/J19710001586","DOIUrl":"https://doi.org/10.1039/J19710001586","url":null,"abstract":"The 1H n.m.r. spectra of NN-dimethyltrifluoroacetamide which have been recorded in various solvents, exhibit two H–F coupling constants which are believed to arise from different coupling mechanisms. The high-temperature rotationally averaged spectrum shows that the two H–F coupling constants have the same sign. The activation parameters for the hindered internal rotation about the central C–N bond have been redetermined by line-shape analysis of the temperature-dependent high-resolution 1H n.m.r. spectra.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":"42 1","pages":"1586-1589"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76671199","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}
引用次数: 4
Carbonyl substitution reactions of chlorotricarbonyl-(π-tetrahydroindenyl)molybdenum: the ‘long-range effect’ of an aromatic ring 氯三羰基-(π-四氢独立基)钼的羰基取代反应:芳环的“远程效应”
Journal of The Chemical Society A: Inorganic, Physical, Theoretical Pub Date : 1971-01-01 DOI: 10.1039/J19710000940
C. White, R. Mawby
{"title":"Carbonyl substitution reactions of chlorotricarbonyl-(π-tetrahydroindenyl)molybdenum: the ‘long-range effect’ of an aromatic ring","authors":"C. White, R. Mawby","doi":"10.1039/J19710000940","DOIUrl":"https://doi.org/10.1039/J19710000940","url":null,"abstract":"The mechanism, rate, and activation parameters for carbonyl substitution reactions of the π-tetrahydroindenyl complex (π-C9H11)Mo(CO)3Cl, but closely similar to those of the π-cyclopentadienyl complex (π-C5H5)Mo(CO)3Cl. This pattern cannot be predicted from the ground-state properties of the three complexes and would not be expected on simple steric grounds. It is suggested that the anomalous behaviour of the π-indenyl complex is due to a stabilizing effect of the six-membered aromatic ring on the transition state for carbonyl substitution reactions.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":"31 1","pages":"940-942"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76671966","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}
引用次数: 9
Crystal structure of [1,2-bis(dimethylarsino)trifluoroethane]tetracarbonylmolybdenum, (Me2AsCHF·CF2AsMe2)Mo(CO)4 [1,2-二甲基三氟乙烷]四羰基钼(Me2AsCHF·CF2AsMe2)Mo(CO)4的晶体结构
Journal of The Chemical Society A: Inorganic, Physical, Theoretical Pub Date : 1971-01-01 DOI: 10.1039/J19710002922
I. W. Nowell, J. Trotter
{"title":"Crystal structure of [1,2-bis(dimethylarsino)trifluoroethane]tetracarbonylmolybdenum, (Me2AsCHF·CF2AsMe2)Mo(CO)4","authors":"I. W. Nowell, J. Trotter","doi":"10.1039/J19710002922","DOIUrl":"https://doi.org/10.1039/J19710002922","url":null,"abstract":"Crystals of [1,2-bis(dimethylarsino)trifluoroethane]tetracarbonylmolybdenum, (Me2AsCHF·CF2AsMe2)Mo(CO)4, are orthorhombic, a= 18·26, b= 14·87, c= 12·52 A, Z= 8, space group Pbca. The structure was determined with Mo-Kα diffractometer data by Patterson, electron-density, and full-matrix least-squares methods, the final R being 0·052 for 1757 observed reflexions. The molybdenum atom has a slightly distorted octahedral co-ordination, with As–Mo–As angle 81·9(1)° and Mo–As bond distances 2·563(2) and 2·589(2)A. The five-membered ring is non-planar, with As–C–C–As dihedral angle 22°, and the hydrogen atom in an equatorial position. The C–C bond distance is extremely short, 1·30(2)A, and the axial C–F bond lengths, 1·72(3) and 1·73(2)A, are very significantly longer than the equatorial C–F bond, 1·38(2)A, and than a normal C–F bond, 1·33 A. The C–C–F-(axial) angles are very far from tetrahedral (85 and 82°). These unusual features can be explained by a contribution from an ionic resonance structure, [(Me2AsCH:CFAsMe2)Mo(CO)4]2+2F–.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":"48 1","pages":"2922-2925"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78282706","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}
引用次数: 3
Carbon compounds of the transition metals. Part XXI. The crystal and molecular structure of bis[tricarbonyl-(3-chloro-2-methylnitrosobenzene)iron] 过渡金属的碳化合物。第二十一章。双[三羰基-(3-氯-2-甲基亚硝基苯)铁]的晶体和分子结构
Journal of The Chemical Society A: Inorganic, Physical, Theoretical Pub Date : 1971-01-01 DOI: 10.1039/J19710000864
M. Barrow, O. S. Mills
{"title":"Carbon compounds of the transition metals. Part XXI. The crystal and molecular structure of bis[tricarbonyl-(3-chloro-2-methylnitrosobenzene)iron]","authors":"M. Barrow, O. S. Mills","doi":"10.1039/J19710000864","DOIUrl":"https://doi.org/10.1039/J19710000864","url":null,"abstract":"The product isolated from the reaction of 3-chloro-2-methylnitrobenzene with pentacarbonyliron is shown to be dimeric and of formula C20H12Cl2N2O8Fe2. Crystals are monoclinic with a= 18·23, b= 7·25, c= 8·71 A(±0·03%)β= 90·85°, spacegroup P21/n(C2h5, No. 14), and Z= 2. The structure was determined from 815 non-zero and visually estimated independent reflexions. The refinement, by large-block matrix least-squares, yielded a final R of 5·8%. The molecules are centrosymmetric with the two iron and two nitrogen atoms coplar. The oxygen atoms lie on either side of this plane in positions such that each is bonded to one iron atom only. Thus the nitroso-groups bridge the iron atoms unsymmetrically. The Fe ⋯ Fe distance is 3·13 A, which corresponds to a null bond.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":"6 1","pages":"864-868"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78561310","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}
引用次数: 15
Transition metal–carbon bonds. Part XXIV. Alkenyl- and allenylplatinum(II) and alkenyl-palladium(II) complexes 过渡金属-碳键。第二十四一部分。烯基和烯基铂(II)和烯基钯(II)配合物
Journal of The Chemical Society A: Inorganic, Physical, Theoretical Pub Date : 1971-01-01 DOI: 10.1039/J19710002667
B. Mann, B. Shaw, N. I. Tucker
{"title":"Transition metal–carbon bonds. Part XXIV. Alkenyl- and allenylplatinum(II) and alkenyl-palladium(II) complexes","authors":"B. Mann, B. Shaw, N. I. Tucker","doi":"10.1039/J19710002667","DOIUrl":"https://doi.org/10.1039/J19710002667","url":null,"abstract":"Acetylene–platinum(0) complexes [Pt(ac)(PPh3)2] react with acids (HX)(X = Cl or OCOCF3) to give alkenyl–platinum(II) complexes of type trans-[PtX(alkenyl)(PPh3)2]. Other alkenyl complexes of this type (X = Br) were made from [Pt(PPh3)x] and vinylic bromides. Hydrazine reduction of cis-[MCl2(PMe2Ph)2](M = Pt or Pd) in the presence of β-bromostyrene gives trans-[MBr(CH:CHPh)(PMe2Ph)2] in poor yields. 1H N.m.r. studies show that in alkenyl complexes, prepared by protonation of acetylene complexes, the added proton and the platinum are cis on the alkenyl double-bond. Protonation also goes in the Markownikoff sense, i.e. [Pt(RC⋮CH)(PPh3)2] gives [PtX(RC:CH2)(PPh3)2]. Some allenyl complexes of the type trans-[PtCl(CH:C:CR1R2)(PPh3)2] were synthesized from Pt(PPh3)3 and prop-2-ynylic halides, HC⋮CC(Cl)R1R2(R1, R2= H, Me or Ph, etc.). Values of the coupling constants J(Pt–H), J(H–H), and J(P–H) are used to confirm the structures and assign the stereochemistry of these complexes. Other 1H and 31P n.m.r. data and also i.r. data are given and discussed.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":"43 1","pages":"2667-2673"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78562201","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}
引用次数: 29
Metal complexes of unsaturated tertiary phosphines and arsines. Part IX. Platinum complexes of tris-olefin-phosphine, -arsine, and -stibine chelate groups 不饱和叔膦和砷的金属配合物。第九部分。三烯烃-膦、-胂和-棘碱螯合基团的铂配合物
Journal of The Chemical Society A: Inorganic, Physical, Theoretical Pub Date : 1971-01-01 DOI: 10.1039/J19710001491
D. I. Hall, R. Nyholm
{"title":"Metal complexes of unsaturated tertiary phosphines and arsines. Part IX. Platinum complexes of tris-olefin-phosphine, -arsine, and -stibine chelate groups","authors":"D. I. Hall, R. Nyholm","doi":"10.1039/J19710001491","DOIUrl":"https://doi.org/10.1039/J19710001491","url":null,"abstract":"Three new ligands, tris-(ortho-vinylphenyl) phosphine (tvpp) and its arsenic (tvpa) and antimony (tvps) analogues, have been prepared and their complexes with platinum(II) investigated: these derivatives have the general formula PtBr2(Ligand), and are monomeric in chloroform. l.r. and Raman spectral studies indicate that in the solid state there are two types of aliphatic C:C bond present. We conclude that one of the double bonds is co-ordinated and the other two are free. 1H n.m.r. data indicate that all three vinyl C:C bonds are equivalent in solution, indicating a rapid, bonded ⇌ non-bonded equilibrium for the ·CH:CH2 groups to the platinum atom. The complexes react with two moles of bromine with saturation of two double bonds to give a platinum(II) compound with one, co-ordinated double bond. A possible reaction mechanism is presented.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":"9 1","pages":"1491-1493"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75003735","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}
引用次数: 12
Thermodynamics of the actinide elements. Part III. Heats of formation of the dicaesium actinide hexachloro-complexes 锕系元素热力学。第三部分。二锕系六氯配合物的生成热
Journal of The Chemical Society A: Inorganic, Physical, Theoretical Pub Date : 1971-01-01 DOI: 10.1039/J19710000841
J. Fuger, D. Brown
{"title":"Thermodynamics of the actinide elements. Part III. Heats of formation of the dicaesium actinide hexachloro-complexes","authors":"J. Fuger, D. Brown","doi":"10.1039/J19710000841","DOIUrl":"https://doi.org/10.1039/J19710000841","url":null,"abstract":"The heats of solution in aqueous hydrochloric acid of the various dicaesium actinide(IV) hexachlorides have been measured at 25·00 ± 0·05°C. For the thorium, protactinium, uranium, neptunium, and plutonium compounds, the values are, in 1M-HCl, –31·37 ± 0·12, –23·94 ± 0·31, –19·91 ± 0·04, –20·16 ± 0·07, and –13·67 ± 0·19 kcal mol–1, respectively, and in 6M-HCl, –20·97 ± 0·06, –12·74 ± 0·24, –8·11 ± 0·05, –7·48 ± 0·10, and –0·18 ± 0·03 kcal mol–1, respectively. The heat of solution of the plutonium compound in 1M-HClO4 is –17·74 ± 0·05 kcal mol–1. Combination of these values with other thermodynamic data yields the following heats of formation at 298°K: Cs2ThCl6(c), –508·7 ± 0·5 kcal mol–1; Cs2UCl6(c)–476·5 ± 1·1 kcal mol–1; Cs2NpCl6(c), –468·5 ± 0·4 kcal mol–1, and Cs2PuCl6(c), –466·9 ± 1·0 kcal mol–1.","PeriodicalId":17321,"journal":{"name":"Journal of The Chemical Society A: Inorganic, Physical, Theoretical","volume":"52 1","pages":"841-846"},"PeriodicalIF":0.0,"publicationDate":"1971-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75097548","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}
引用次数: 8
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