The asymmetric ‘tripod’ ligands N-[2-(diphenylphosphino)ethyl]-N-(2-methoxyethyl)-N′N′- diethylthylenediamine (I; donor set N2OP) and N-[2-(diphenylphosphino)ethyl)-N-[2-(methylthio)ethyl]-N′N′-diethylethylenediamine (II; donor set N2SP) form cobalt(II) and nickel(II) complexes with general formula [MLX]BPh4(X = halogen or NCS). The cobalt(II) complexes are high-spin and five-co-ordinate, probably trigonal bipyramidal, both in the solid state and in solution. The [NiLX]BPh4 complexes with L =(I), X = l or NCS are low-spin and probably five-co-ordinate in the solid state with a distorted square-pyramidal stereochemistry. All the other nickel complexes are thought to have a square-planar structure with the ligand L being terdentate with an NNP donor set. The complex [Ni(NOAs2)l]BPh4 derived from the ligand NN-bis-(2-diphenylarsinoethyl)-2-methoxyethylamine (III; donor set NOAs2) is accorded a five-co-ordinate, ‘elongated’ square-pyramidal structure.
不对称“三脚架”配体N-[2-(二苯基膦)乙基]-N-(2-甲氧基乙基)-N ' N ' -二乙二胺(I;N-[2-(二苯基膦)乙基]-N -[2-(甲基硫)乙基]-N ' N ' -二乙基乙二胺(II);用通式[MLX]BPh4(X =卤素或NCS)形成钴(II)和镍(II)配合物。钴(II)配合物在固体和溶液中都是高自旋和五坐标的，可能是三角双锥体。L =(I)， X = L或NCS的[NiLX]BPh4配合物具有低自旋和可能的五坐标固相，具有扭曲的方锥体立体化学。所有其他的镍配合物被认为具有方形平面结构，配体L与NNP给体集是三齿合的。配合物[Ni(NOAs2) 1]BPh4由配体nn -二-(2-二苯larsinethyl)-2-甲氧基乙胺(III;供体集NOAs2)被赋予一个五坐标，“拉长”的方形金字塔结构。
{"title":"Five-co-ordination with ‘hybrid’ ligands. Part VII. Cobalt(II) and nickel(II) complexes with asymmetric tripod ligands having N2OP, N2SP, and NOAs2 donor sets","authors":"R. Morassi, L. Sacconi","doi":"10.1039/J19710001487","DOIUrl":"https://doi.org/10.1039/J19710001487","url":null,"abstract":"The asymmetric ‘tripod’ ligands N-[2-(diphenylphosphino)ethyl]-N-(2-methoxyethyl)-N′N′- diethylthylenediamine (I; donor set N2OP) and N-[2-(diphenylphosphino)ethyl)-N-[2-(methylthio)ethyl]-N′N′-diethylethylenediamine (II; donor set N2SP) form cobalt(II) and nickel(II) complexes with general formula [MLX]BPh4(X = halogen or NCS). The cobalt(II) complexes are high-spin and five-co-ordinate, probably trigonal bipyramidal, both in the solid state and in solution. The [NiLX]BPh4 complexes with L =(I), X = l or NCS are low-spin and probably five-co-ordinate in the solid state with a distorted square-pyramidal stereochemistry. All the other nickel complexes are thought to have a square-planar structure with the ligand L being terdentate with an NNP donor set. The complex [Ni(NOAs2)l]BPh4 derived from the ligand NN-bis-(2-diphenylarsinoethyl)-2-methoxyethylamine (III; donor set NOAs2) is accorded a five-co-ordinate, ‘elongated’ square-pyramidal structure.","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":"84086428","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 i.r. and Raman spectra of the series of dihalogeno(methyl)germanes, MeGeHX2(X = F, Cl, Br, I) and their specifically deuteriated analogues, MeGeDX2, are recorded. A normal co-ordinate treatment based on a modified valence force field confirms the assignment of 17 of the 18 fundamental frequencies for each molecule. The torsional mode is not observed. The transferability of the force constants between the protonated and deuteriated species is tested.
{"title":"The vibrational spectra of silane and germane derivatives. Part V. The infrared and Raman spectra of dihalogeno(methyl)germanes","authors":"G. K. Barker, J. Drake, R. Hemmings, B. Rapp","doi":"10.1039/J19710003291","DOIUrl":"https://doi.org/10.1039/J19710003291","url":null,"abstract":"The i.r. and Raman spectra of the series of dihalogeno(methyl)germanes, MeGeHX2(X = F, Cl, Br, I) and their specifically deuteriated analogues, MeGeDX2, are recorded. A normal co-ordinate treatment based on a modified valence force field confirms the assignment of 17 of the 18 fundamental frequencies for each molecule. The torsional mode is not observed. The transferability of the force constants between the protonated and deuteriated species is tested.","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":"78532986","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 crystal structure of the 1 : 1 complex of 8-hydroxyquinoline and 1,3,5-trinitrobenzene has been determined by three-dimensional X-ray methods. It is a plane-to-plane π–π* electron donor–acceptor complex formed from dimeric 8-hydroxyquinoline molecules as electron donors and 1,3,5-trinitrobenzene molecules as acceptors. In the stacks of alternating donor and acceptor molecules, each 1,3,5-trinitrobenzene molecule is located in the position of maximum π–π* overlap with respect to one of its neighbouring 8-hydroxyquinoline molecules and somewhat shifted from that position with respect to the other.The 8-hydroxyquinoline dimer is held together by a bifurcated hydrogen-bond system similar to that in the 8-hydroxyquinoline–chloranil complex.
{"title":"Molecular complexes. Part X. The crystal and molecular structure of the 1 : 1 complex of 8-hydroxyquinoline and 1,3,5-trinitrobenzene","authors":"E. Castellano, C. Prout","doi":"10.1039/J19710000550","DOIUrl":"https://doi.org/10.1039/J19710000550","url":null,"abstract":"The crystal structure of the 1 : 1 complex of 8-hydroxyquinoline and 1,3,5-trinitrobenzene has been determined by three-dimensional X-ray methods. It is a plane-to-plane π–π* electron donor–acceptor complex formed from dimeric 8-hydroxyquinoline molecules as electron donors and 1,3,5-trinitrobenzene molecules as acceptors. In the stacks of alternating donor and acceptor molecules, each 1,3,5-trinitrobenzene molecule is located in the position of maximum π–π* overlap with respect to one of its neighbouring 8-hydroxyquinoline molecules and somewhat shifted from that position with respect to the other.The 8-hydroxyquinoline dimer is held together by a bifurcated hydrogen-bond system similar to that in the 8-hydroxyquinoline–chloranil complex.","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":"78545878","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 temperature-dependence of the extraction coefficients of different organic solvents for metals, such as gallium and iron, from aqueous hydrochloric acid solutions, has been shown to depend on the metal concentration. The data have been analysed to yield entropies and enthalpies of dissociation of the extracting acids in the organic phase. The peculiarities of the values obtained are discussed.
{"title":"Solvent extraction from halide solutions. Part V. Temperature-dependence and dissociation of ion pairs","authors":"Z. Maksimović, A. Maddock","doi":"10.1039/J19710000650","DOIUrl":"https://doi.org/10.1039/J19710000650","url":null,"abstract":"The temperature-dependence of the extraction coefficients of different organic solvents for metals, such as gallium and iron, from aqueous hydrochloric acid solutions, has been shown to depend on the metal concentration. The data have been analysed to yield entropies and enthalpies of dissociation of the extracting acids in the organic phase. The peculiarities of the values obtained 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":"77458233","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 polarised far-i.r. reflectance spectra of A2CuCl4,2H2O (A = NH4, K, or Rb) single crystals have been recorded in the region 40–400 cm–1. These have permitted the observation and assignment of most of the predicted bands, including one at ca. 180 cm–1 due predominantly to the ‘long’ Cu–Cl stretching mode. Anomalies in the reflectance spectra of (111) faces of these crystals are discussed.
偏振的远红外线。A2CuCl4,2H2O (A = NH4, K，或Rb)单晶的反射光谱在40-400 cm-1范围内。这使得大多数预测波段的观测和分配成为可能，包括一个大约180 cm-1的波段，主要是由于“长”Cu-Cl拉伸模式。讨论了这些晶体(111)面反射光谱中的异常现象。
{"title":"Far-infrared reflectance spectra of A2CuCl4,2H2O (A = NH4, K, or Rb) single crystals: copper–chlorine vibrations of the distorted octahedral aquochlorocuprate(II) anion","authors":"J. Dunsmuir, A. Lane","doi":"10.1039/J19710002724","DOIUrl":"https://doi.org/10.1039/J19710002724","url":null,"abstract":"The polarised far-i.r. reflectance spectra of A2CuCl4,2H2O (A = NH4, K, or Rb) single crystals have been recorded in the region 40–400 cm–1. These have permitted the observation and assignment of most of the predicted bands, including one at ca. 180 cm–1 due predominantly to the ‘long’ Cu–Cl stretching mode. Anomalies in the reflectance spectra of (111) faces of these crystals 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":"78034073","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 compound previously formulated as (π-C5H5)Fe(CO)2Sn(Ph)(OSOPh)(OH) has been shown, by X-ray analysis, to be a centrosymmetric dimer with two five-co-ordinate tin atoms linked by a dihydroxo-bridge. The Sn–O bond lengths are 2·054(2)A and the O–Sn–O and Sn–O–Sn bond angles are 70·8(1) and 109·2(1)°, respectively. The Sn–Fe bond distance of 2·499(1)A is ca. 0·03 A longer than the limiting value for this bond type and is presumed to be a σ-bond. Other bond distances of interest are Sn–O(non-bridging) 2·206(2), Sn–C 2·146(3), Fe–C(carbonyl) 1·765(4), Fe–C(ring) 2·093(4), CO 1·142(5), S–O 1·539(3), SO 1·499(3), and S–C 1·808(4)A.Crystals of the dimer are monoclinic with cell dimensions a= 9·698(2)b= 18·097(3), c= 13·516(4)A, β= 123·44(3)°, space group P21/c, and Z= 2. The structure analysis, based on 2592 independent intensities measured by counter diffractometry, was carried out by the heavy-atom method and refinement was by least-squares techniques to a final R of 0·024.
{"title":"Metal–metal bonding in co-ordination complexes. Part XI. Crystal and molecular structure of di[(benzenesulphinato)-µ-hydroxo-phenylstannio]-tetracarbonyldi-π-cyclopentadienyl-di-iron","authors":"R. Restivo, R. Bryan","doi":"10.1039/J19710003364","DOIUrl":"https://doi.org/10.1039/J19710003364","url":null,"abstract":"The compound previously formulated as (π-C5H5)Fe(CO)2Sn(Ph)(OSOPh)(OH) has been shown, by X-ray analysis, to be a centrosymmetric dimer with two five-co-ordinate tin atoms linked by a dihydroxo-bridge. The Sn–O bond lengths are 2·054(2)A and the O–Sn–O and Sn–O–Sn bond angles are 70·8(1) and 109·2(1)°, respectively. The Sn–Fe bond distance of 2·499(1)A is ca. 0·03 A longer than the limiting value for this bond type and is presumed to be a σ-bond. Other bond distances of interest are Sn–O(non-bridging) 2·206(2), Sn–C 2·146(3), Fe–C(carbonyl) 1·765(4), Fe–C(ring) 2·093(4), CO 1·142(5), S–O 1·539(3), SO 1·499(3), and S–C 1·808(4)A.Crystals of the dimer are monoclinic with cell dimensions a= 9·698(2)b= 18·097(3), c= 13·516(4)A, β= 123·44(3)°, space group P21/c, and Z= 2. The structure analysis, based on 2592 independent intensities measured by counter diffractometry, was carried out by the heavy-atom method and refinement was by least-squares techniques to a final R of 0·024.","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":"78055828","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}
Barium sulphate doped with various alkali-metal salts gave, on exposure to 60Co γ-rays at 77 K, two types of trapped hydrogen atoms, one of which had e.s.r. spectra characterised by hyperfine coupling to the alkali-metal cations. For example, the species NaH+ had gav= 2·0013, a‖(1H)= 513·2 G, a⊥(1H)= 510·7 G, a‖(23Na)= 21·4 G and a⊥(23Na)= 15·1 G.These results, together with data for other host crystals, are discussed in terms of the structure of the adducts and their stability.
{"title":"Unstable intermediates. Part LXXXVIII. Alkali-metal interaction with trapped hydrogen atoms in barium sulphate","authors":"M. Bloom, R. Eachus, M. Symons","doi":"10.1039/J19710000833","DOIUrl":"https://doi.org/10.1039/J19710000833","url":null,"abstract":"Barium sulphate doped with various alkali-metal salts gave, on exposure to 60Co γ-rays at 77 K, two types of trapped hydrogen atoms, one of which had e.s.r. spectra characterised by hyperfine coupling to the alkali-metal cations. For example, the species NaH+ had gav= 2·0013, a‖(1H)= 513·2 G, a⊥(1H)= 510·7 G, a‖(23Na)= 21·4 G and a⊥(23Na)= 15·1 G.These results, together with data for other host crystals, are discussed in terms of the structure of the adducts and their stability.","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":"72908785","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 carbonylmetal anion [Rh(CO)2(PPh3)2]– has been shown to be a strong nucleophile of similar power to that of [(π-C5H5)Fe(CO)2]– or [(π-C5H5)Ru(CO)2]–. Its reactions with the compounds C6F6, C6F5X (X = CN or CO2Et), (NC)2C6F4, C5F5N, and 2-(NC)C5F4N to afford some new perfluoroaromatic rhodium(l) complexes are discussed.
{"title":"Metal carbonyl chemistry. Part XV. Reactions of the dicarbonylbis-(triphenylphosphine)rhodate anion, [Rh(CO)2(PPh3)2]–, with some perfluoroaromatic compounds","authors":"B. Booth, R. Haszeldine, Ian Perkins","doi":"10.1039/J19710000927","DOIUrl":"https://doi.org/10.1039/J19710000927","url":null,"abstract":"The carbonylmetal anion [Rh(CO)2(PPh3)2]– has been shown to be a strong nucleophile of similar power to that of [(π-C5H5)Fe(CO)2]– or [(π-C5H5)Ru(CO)2]–. Its reactions with the compounds C6F6, C6F5X (X = CN or CO2Et), (NC)2C6F4, C5F5N, and 2-(NC)C5F4N to afford some new perfluoroaromatic rhodium(l) 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":"72909877","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}
Transport numbers for the thiocyanate anion constituent of KCNS in anhydrous acetone have been measured by a conductimetric moving-boundary method at 25 °C. The limiting transport number obtained is t°CNS–= 0·6237 ± 0·0009. Limiting ion conductances in acetone have been calculated and discussed.
{"title":"Solutions in acetone. Part II. Transference numbers of potassium thiocyanate and ionic conductances in acetone at 25 °C","authors":"H. Brookes, M. Hotz, A. Spong","doi":"10.1039/J19710002415","DOIUrl":"https://doi.org/10.1039/J19710002415","url":null,"abstract":"Transport numbers for the thiocyanate anion constituent of KCNS in anhydrous acetone have been measured by a conductimetric moving-boundary method at 25 °C. The limiting transport number obtained is t°CNS–= 0·6237 ± 0·0009. Limiting ion conductances in acetone have been calculated and 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":"73182208","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 Mossbauer spectra of cyclohexyltin derivatives and of the compounds Ph2Sn(X)·[CH2]4·Sn(X)Ph2(X = I, OH, O·CO·Me, or Ph), BunSn(O·CO·Me)4–n(n= 2 or 3), and Bu2Sn maleate have been recorded. These data are used to define the range of quadrupole splittings associated with tetrahedral organotin compounds. It is shown that the simple point-charge model does not account for the quadrupole splittings of compounds with differing co-ordination numbers. Quadrupole splitting data are used empirically to discuss intermolecular association in organotin compounds.
{"title":"Mössbauer spectra and structures of organotin compounds. The relationship between quadrupole splitting and intermolecular association","authors":"A. Maddock, R. H. Platt","doi":"10.1039/J19710001191","DOIUrl":"https://doi.org/10.1039/J19710001191","url":null,"abstract":"The Mossbauer spectra of cyclohexyltin derivatives and of the compounds Ph2Sn(X)·[CH2]4·Sn(X)Ph2(X = I, OH, O·CO·Me, or Ph), BunSn(O·CO·Me)4–n(n= 2 or 3), and Bu2Sn maleate have been recorded. These data are used to define the range of quadrupole splittings associated with tetrahedral organotin compounds. It is shown that the simple point-charge model does not account for the quadrupole splittings of compounds with differing co-ordination numbers. Quadrupole splitting data are used empirically to discuss intermolecular association in organotin compounds.","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":"80117209","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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