首页 > 最新文献

Journal of The Chemical Society A: Inorganic, Physical, Theoretical最新文献

英文 中文
Infrared and electron spin resonance studies of the effect of γ-irradiation on [Cr(CN)5NO]3–, [Mn(CN)5NO]3–, and [Fe(CN)5NO]2– in alkali-metal halide host lattices 红外和电子自旋共振研究了γ辐照对碱金属卤化物基体晶格中[Cr(CN)5NO]3 -、[Mn(CN)5NO]3 -和[Fe(CN)5NO]2 -的影响
Pub Date : 1971-01-01 DOI: 10.1039/J19710003212
M. Bloom, J. Raynor, K. Root, M. Symons
I.r. and e.s.r. spectra of γ-irradiated [Cr(CN)5NO]3–, [Mn(CN)5NO]3–, and [Fe(CN)5NO]2– in alkali-metal halide host lattices are reported. New i.r. absorptions are attributed to species resembling [Cr(CN)5NO]4–and 5– and [Mn(CN)5NO]2–and 4–. There is e.s.r. evidence for the formation of [Mn(CN)5NO]2– and [Fe(CN)5NO]3– ions, but no feature attributable to [Cr(CN)5NO]5– or [Mn(CN)5NO]4– was detected. Possible reasons for this apparent contradiction are discussed. There was evidence for the metal ion in [Mn(CN)5NO]3– migrating though the lattice to sites where it could exist in the high-spin d5 form.
报道了γ辐照[Cr(CN)5NO]3 -、[Mn(CN)5NO]3 -和[Fe(CN)5NO]2 -在碱金属卤化物基体晶格中的红外光谱和e.s.r.光谱。新的红外吸收归因于类似[Cr(CN)5NO]4 -和5 -和[Mn(CN)5NO]2 -和4 -的物质。有esr证据表明[Mn(CN)5NO]2 -和[Fe(CN)5NO]3 -离子的形成,但未检测到[Cr(CN)5NO]5 -或[Mn(CN)5NO]4 -的特征。讨论了这种明显矛盾的可能原因。有证据表明[Mn(CN)5NO]3 -中的金属离子通过晶格迁移到它可以以高自旋d5形式存在的位置。
{"title":"Infrared and electron spin resonance studies of the effect of γ-irradiation on [Cr(CN)5NO]3–, [Mn(CN)5NO]3–, and [Fe(CN)5NO]2– in alkali-metal halide host lattices","authors":"M. Bloom, J. Raynor, K. Root, M. Symons","doi":"10.1039/J19710003212","DOIUrl":"https://doi.org/10.1039/J19710003212","url":null,"abstract":"I.r. and e.s.r. spectra of γ-irradiated [Cr(CN)5NO]3–, [Mn(CN)5NO]3–, and [Fe(CN)5NO]2– in alkali-metal halide host lattices are reported. New i.r. absorptions are attributed to species resembling [Cr(CN)5NO]4–and 5– and [Mn(CN)5NO]2–and 4–. There is e.s.r. evidence for the formation of [Mn(CN)5NO]2– and [Fe(CN)5NO]3– ions, but no feature attributable to [Cr(CN)5NO]5– or [Mn(CN)5NO]4– was detected. Possible reasons for this apparent contradiction are discussed. There was evidence for the metal ion in [Mn(CN)5NO]3– migrating though the lattice to sites where it could exist in the high-spin d5 form.","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":"80182847","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
Magnetic properties of cobalt(II) complexes. Part III. Crystal magnetic anisotropy of α-dichlorobis(pyridine)cobalt(II) 钴(II)配合物的磁性能。第三部分。α-二氯(吡啶)钴(II)晶体磁性各向异性
Pub Date : 1971-01-01 DOI: 10.1039/J19710003751
R. Bentley, M. Gerloch, J. Lewis, P. Quested
The principal and mean magnetic susceptibilities of Co(py)2Cl2(py = pyridine) have been measured in the temperature range 300–80 K. They are characterized by an interesting anomaly at ca. 150 K when the crystal anisotropy in the ab plane abruptly changes sign. There is an associated transition in the anisotropy in the bc plane but none is observed for mean moments. The overall effect on principal molecular magnetic moments appears sufficiently small, however, not to interfere with the theoretical interpretation of the magnetism of Co(py)2Cl2 within the framework of a tetragonally squashed octahedron. The mean moment of Co(py)2Cl2 at room temperature is well known to be high compared with other ‘octahedral’ cobalt(II) ions and a discussion of this phenomenon in terms of the sense of tetragonality is presented as are some general comparisons with the preceding paper.
测定了Co(py)2Cl2(py =吡啶)在300 ~ 80k温度范围内的主磁化率和平均磁化率。它们的特征是在约150k时,ab面晶体各向异性突然改变符号。在bc平面的各向异性中有一个相关的转变,但在平均矩中没有观察到。然而,对主分子磁矩的总体影响似乎足够小,不会干扰Co(py)2Cl2在四方压扁的八面体框架内的磁性的理论解释。众所周知,Co(py)2Cl2在室温下的平均矩与其他“八面体”钴(II)离子相比是高的,本文从四面体的角度对这一现象进行了讨论,并与前一篇论文进行了一般性比较。
{"title":"Magnetic properties of cobalt(II) complexes. Part III. Crystal magnetic anisotropy of α-dichlorobis(pyridine)cobalt(II)","authors":"R. Bentley, M. Gerloch, J. Lewis, P. Quested","doi":"10.1039/J19710003751","DOIUrl":"https://doi.org/10.1039/J19710003751","url":null,"abstract":"The principal and mean magnetic susceptibilities of Co(py)2Cl2(py = pyridine) have been measured in the temperature range 300–80 K. They are characterized by an interesting anomaly at ca. 150 K when the crystal anisotropy in the ab plane abruptly changes sign. There is an associated transition in the anisotropy in the bc plane but none is observed for mean moments. The overall effect on principal molecular magnetic moments appears sufficiently small, however, not to interfere with the theoretical interpretation of the magnetism of Co(py)2Cl2 within the framework of a tetragonally squashed octahedron. The mean moment of Co(py)2Cl2 at room temperature is well known to be high compared with other ‘octahedral’ cobalt(II) ions and a discussion of this phenomenon in terms of the sense of tetragonality is presented as are some general comparisons with the preceding paper.","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":"80345690","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: 6
The chemistry of vitamin B12. Part XII. The co-ordination of nitrogenous bases 维生素B12的化学成分。第十二部分。氮基的配位
Pub Date : 1971-01-01 DOI: 10.1039/J19710000196
G. C. Hayward, H. Hill, J. M. Pratt, ROBERT J. P. Williams
Formation constants have been determined for the substitution of co-ordinated water in diaquocobinamide by ammonia and imidazole, in aquocobalamin by ammonia, and in cyanoaquocobinamide by ammonia, pyridine, imidazole, benzimidazole, and adenine; the last three bases can co-ordinate in the conjugate anion form. It is shown that the formation constants for the binding of ammonia are more sensitive to the nature of the trans-ligand than those for the binding of imidazole, and that the relative order of their formation constants can change as the trans-ligand is varied. Pseudo-first-order rate constants for the substitution of co-ordinated ammonia by water at 30° have been obtained for corrinoids with the following trans-ligands: H2O, 1·4 × 10-5 s–1; 5,6-dimethylbenzimidazole, 8·6 × 10-5 s–1; CN–, SO32–, and CH3–, 3 × 10–1 s–1. The order of ligands observed in the kinetic trans-effect parallels that for the thermodynamic trans-effect.
测定了氨和咪唑取代二甲钴胺中的配位水,氨取代氨基钴胺中的配位水,以及氨、吡啶、咪唑、苯并咪唑和腺嘌呤取代氰钴酰胺中的配位水的形成常数;后三个碱能以共轭阴离子形式配位。结果表明,氨结合的形成常数对反式配体的性质比咪唑结合的形成常数更敏感,并且它们的形成常数的相对顺序可以随着反式配体的变化而变化。在30°温度下,得到了配体为H2O, 1·4 × 10-5 s-1的拟一阶速率常数;5,6-二甲基苯并咪唑,8·6 × 10-5 s-1;CN -, SO32 -和CH3 -, 3 × 10-1 s-1。在动力学反式效应中观察到的配体顺序与热力学反式效应相似。
{"title":"The chemistry of vitamin B12. Part XII. The co-ordination of nitrogenous bases","authors":"G. C. Hayward, H. Hill, J. M. Pratt, ROBERT J. P. Williams","doi":"10.1039/J19710000196","DOIUrl":"https://doi.org/10.1039/J19710000196","url":null,"abstract":"Formation constants have been determined for the substitution of co-ordinated water in diaquocobinamide by ammonia and imidazole, in aquocobalamin by ammonia, and in cyanoaquocobinamide by ammonia, pyridine, imidazole, benzimidazole, and adenine; the last three bases can co-ordinate in the conjugate anion form. It is shown that the formation constants for the binding of ammonia are more sensitive to the nature of the trans-ligand than those for the binding of imidazole, and that the relative order of their formation constants can change as the trans-ligand is varied. Pseudo-first-order rate constants for the substitution of co-ordinated ammonia by water at 30° have been obtained for corrinoids with the following trans-ligands: H2O, 1·4 × 10-5 s–1; 5,6-dimethylbenzimidazole, 8·6 × 10-5 s–1; CN–, SO32–, and CH3–, 3 × 10–1 s–1. The order of ligands observed in the kinetic trans-effect parallels that for the thermodynamic trans-effect.","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":"80352272","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
Mechanism of the reaction of vanadium(III) with mercury(II) in aqueous perchloric acid solutions 钒(III)与汞(II)在高氯酸水溶液中的反应机理
Pub Date : 1971-01-01 DOI: 10.1039/J19710003068
M. Green, W. Higginson, J. Stead, A. Sykes
Kinetic studies on the reaction of vanadium(III) with mercury(II), 2VIII+ 2HgII→ 2VIV+(HgI)2, in perchloric acid solutions of ionic strengths 2·0M(LiClO4) and 3·0M(NaClO4) are consistent with the mechanism (i)–(iii). VIII+ HgII [graphic omitted] VIV+ HgI(i), VIII+ HgI [graphic omitted] VIV+ Hg0(ii), VIV+ HgI [graphic omitted] VV+ Hg0(iii), Subsequent reactions Hg0+ HgII→(HgI)2, and VIII+ VV→ 2VIV are more rapid and are not rate determining. The rate law corresponding to (i)–(iii) is given by (iv). At low initial vanadium(IV) concentrations the [graphic omitted] second term in (iv) is negligible, but at high vanadium(IV) concentrations (>0·1M) the second term becomes dominant. Although the kinetics do not rule out the two-electron reaction VIII+ HgII→ VV+ Hg0 as an alternative to (iii), the consecutive one-electron changes V3+→ VO2+→ VO2+ are considered more likely.
在离子强度为2.0 m(LiClO4)和3.0 m(NaClO4)的高氯酸溶液中,钒(III)与汞(II), 2VIII+ 2HgII→2VIV+(HgI)2的反应动力学研究符合(i) - (III)的机理。VIII+ HgII[图略]VIV+ HgI(i), VIII+ HgI[图略]VIV+ Hg0(ii), VIV+ HgI[图略]VV+ Hg0(iii),后续反应Hg0+ HgII→(HgI)2和VIII+ VV→2VIV更快速,不决定速率。(i) - (iii)对应的速率定律由(iv)给出。在初始钒(iv)浓度较低时,(iv)中的第二项可以忽略不计,但在钒(iv)浓度较高时(>0·1M),第二项起主导作用。虽然动力学不排除两电子反应VIII+ HgII→VV+ Hg0可以替代(iii),但连续的单电子反应V3+→VO2+→VO2+的可能性更大。
{"title":"Mechanism of the reaction of vanadium(III) with mercury(II) in aqueous perchloric acid solutions","authors":"M. Green, W. Higginson, J. Stead, A. Sykes","doi":"10.1039/J19710003068","DOIUrl":"https://doi.org/10.1039/J19710003068","url":null,"abstract":"Kinetic studies on the reaction of vanadium(III) with mercury(II), 2VIII+ 2HgII→ 2VIV+(HgI)2, in perchloric acid solutions of ionic strengths 2·0M(LiClO4) and 3·0M(NaClO4) are consistent with the mechanism (i)–(iii). VIII+ HgII [graphic omitted] VIV+ HgI(i), VIII+ HgI [graphic omitted] VIV+ Hg0(ii), VIV+ HgI [graphic omitted] VV+ Hg0(iii), Subsequent reactions Hg0+ HgII→(HgI)2, and VIII+ VV→ 2VIV are more rapid and are not rate determining. The rate law corresponding to (i)–(iii) is given by (iv). At low initial vanadium(IV) concentrations the [graphic omitted] second term in (iv) is negligible, but at high vanadium(IV) concentrations (>0·1M) the second term becomes dominant. Although the kinetics do not rule out the two-electron reaction VIII+ HgII→ VV+ Hg0 as an alternative to (iii), the consecutive one-electron changes V3+→ VO2+→ VO2+ are considered more likely.","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":"82092815","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: 0
Crystal and molecular structure of dicarbonyl-π-cyclopentadienyliodo[tri(n-butyl)phosphine]molybdenum(II) 二羰基-π-环戊二烯二氧基[三(正丁基)膦]钼(II)的晶体和分子结构
Pub Date : 1971-01-01 DOI: 10.1039/J19710003312
R. Fenn, J. Cross
The title compound crystallises in the space group P42/n(C4h4), with Z= 8, in a unit cell of dimensions: a=b= 19·704 ± 0·006, c= 11·736 ± 0·008 A. The structure was solved from visually estimated photographic data by the heavy-atom method, and refined to R 11·1% for 938 independent reflections. The molecule has a sandwich-type configuration with the cyclopentadienyl ring on one side of the molybdenum, and the other ligands, which are roughly square planar, lying on the other side. The carbonyls are mutually cis.
标题化合物在空间群P42/n(C4h4)中结晶,Z= 8,尺寸为a=b= 19.704±0.006,c= 11.736±0.008 a。用重原子法从视觉估计的照片数据中求解出该结构,并在938个独立反射下将其细化为R 11.1%。该分子具有三明治型结构,环戊二烯环位于钼的一侧,而其他配体大致呈方形平面,位于另一侧。羰基是相互顺式的。
{"title":"Crystal and molecular structure of dicarbonyl-π-cyclopentadienyliodo[tri(n-butyl)phosphine]molybdenum(II)","authors":"R. Fenn, J. Cross","doi":"10.1039/J19710003312","DOIUrl":"https://doi.org/10.1039/J19710003312","url":null,"abstract":"The title compound crystallises in the space group P42/n(C4h4), with Z= 8, in a unit cell of dimensions: a=b= 19·704 ± 0·006, c= 11·736 ± 0·008 A. The structure was solved from visually estimated photographic data by the heavy-atom method, and refined to R 11·1% for 938 independent reflections. The molecule has a sandwich-type configuration with the cyclopentadienyl ring on one side of the molybdenum, and the other ligands, which are roughly square planar, lying on the other side. The carbonyls are mutually cis.","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":"82151890","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: 7
Reduction of buta-1,3-diene by the hexacyanodinickelate(I) anion 六氰丁酸盐(I)阴离子还原丁酸-1,3-二烯
Pub Date : 1971-01-01 DOI: 10.1039/J19710001782
D. Bingham, M. G. Burnett
The kinetics of the reaction of buta-1,3-diene with an aqueous solution of sodium hexacyanodinickelate(I) and the subsequent formation of butenes have been studied at 25° and at an ionic strength of 1·1. The kinetics of the removal of butadiene show that the slow step in complex formation is reaction (i), in which ki= 1·4 ± 0·1 l mol–1 s–1. The kinetics of the formation of the butenes are interpreted in terms of the rate-controlling reduction of two Ni2(CN)64–+ C4H6→(π-C4H6)Ni2(CN)64–(i), cyano-nickel intermediates, π1 and π2, containing a π-1-methylallyl ligand and a π-buta-1,3-diene ligand respectively. The two intermediates react by kinetically distinct paths yielding predominantly trans-but-2-ene, (π1), and cis-but-2-ene, (π2). The presence of a π-1-methylallylnickel complex in the reaction mixture has been confirmed by n.m.r. spectroscopy.
研究了丁烯-1,3-二烯在25°和离子强度为1·1的条件下与六氰丁酸钠(I)水溶液的反应动力学及丁烯的生成。丁二烯脱除动力学表明,络合物形成的慢步是反应(i),其中ki= 1.4±0.1 l mol-1 s-1。丁烯的形成动力学由两个Ni2(CN)64 - + C4H6→(π-C4H6)Ni2(CN)64 - (i),含π-1-甲基烯丙基配体和π- buta1,3 -二烯配体的氰基镍中间体π1和π2的控制速率还原来解释。这两种中间体通过不同的动力学途径反应,主要生成反式-2-丁烯(π - 1)和顺式-2-丁烯(π -2)。用核磁共振光谱证实了反应混合物中π-1-甲基烯丙基镍配合物的存在。
{"title":"Reduction of buta-1,3-diene by the hexacyanodinickelate(I) anion","authors":"D. Bingham, M. G. Burnett","doi":"10.1039/J19710001782","DOIUrl":"https://doi.org/10.1039/J19710001782","url":null,"abstract":"The kinetics of the reaction of buta-1,3-diene with an aqueous solution of sodium hexacyanodinickelate(I) and the subsequent formation of butenes have been studied at 25° and at an ionic strength of 1·1. The kinetics of the removal of butadiene show that the slow step in complex formation is reaction (i), in which ki= 1·4 ± 0·1 l mol–1 s–1. The kinetics of the formation of the butenes are interpreted in terms of the rate-controlling reduction of two Ni2(CN)64–+ C4H6→(π-C4H6)Ni2(CN)64–(i), cyano-nickel intermediates, π1 and π2, containing a π-1-methylallyl ligand and a π-buta-1,3-diene ligand respectively. The two intermediates react by kinetically distinct paths yielding predominantly trans-but-2-ene, (π1), and cis-but-2-ene, (π2). The presence of a π-1-methylallylnickel complex in the reaction mixture has been confirmed by n.m.r. spectroscopy.","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":"82207341","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: 6
Ionic radii from a continuum model for alkali-metal halide lattices 碱金属卤化物晶格的连续介质模型的离子半径
Pub Date : 1971-01-01 DOI: 10.1039/J19710000608
D. Rosseinsky
Application of a long-advocated sphere-in-continuum model to MX lattices yields halide radii in good agreement with those actually observed in diffraction studies. Not only do the mean values agree, but observed fluctuations from constancy are reflected in the individual values calculated for each MX, a second-order effect.
将长期提倡的连续球模型应用于MX晶格,得到的卤化物半径与衍射研究中实际观察到的结果非常吻合。不仅平均值一致,而且观测到的恒定波动也反映在为每个MX计算的单个值中,这是一种二阶效应。
{"title":"Ionic radii from a continuum model for alkali-metal halide lattices","authors":"D. Rosseinsky","doi":"10.1039/J19710000608","DOIUrl":"https://doi.org/10.1039/J19710000608","url":null,"abstract":"Application of a long-advocated sphere-in-continuum model to MX lattices yields halide radii in good agreement with those actually observed in diffraction studies. Not only do the mean values agree, but observed fluctuations from constancy are reflected in the individual values calculated for each MX, a second-order effect.","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":"81301533","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: 0
Dipyrromethene complexes of transition metals. Part II. Stereochemistry of complexes of cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II), mercury(II), and palladium(II) and crystal structure analysis of the palladium complex 过渡金属的二吡咯甲烷配合物。第二部分。钴(II)、镍(II)、铜(II)、锌(II)、镉(II)、汞(II)、钯(II)配合物的立体化学及钯配合物的晶体结构分析
Pub Date : 1971-01-01 DOI: 10.1039/J19710000440
F. C. March, D. A. Couch, K. Emerson, J. Fergusson, W. Robinson
Complexes have been formed between bivalent ions of cobalt, nickel, copper, zinc, mercury, and palladium and the the ligands 4,4′-dicarboxyethyl-3,3′,5,5′-tetramethyldipyrromethene (mpmH) and 3,4′-dicarboxyethyl-5-chloro-3′,4,5′-trimethyldipyrromethene (cpmH). The stereochemistry of these complexes has been investigated by measurement of magnetic susceptibility, and 1H n.m.r. spectra, and u.v. visible spectra. An X-ray determination of the crystal and molecular structure of the complex Pd(mpm)2 is reported. The palladium atom lies on a crystallographic centre of symmetry and is necessarily coplanar with the four co-ordinated nitrogen atoms of the ligand. The unique bidentate ligand is not planar.
钴、镍、铜、锌、汞和钯的二价离子与4,4 ' -二羧基乙基-3,3 ',5,5 ' -四甲基二吡咯甲烷(mpmH)和3,4 ' -二羧基乙基-5-氯-3 ',4,5 ' -三甲基二吡咯甲烷(cpmH)形成配合物。通过磁化率测量、1H nmr光谱和紫外可见光谱研究了这些配合物的立体化学性质。本文报道了配合物Pd(mpm)2的晶体和分子结构的x射线测定。钯原子位于对称的晶体中心,必然与配体的四个配位氮原子共面。独特的双齿配体不是平面的。
{"title":"Dipyrromethene complexes of transition metals. Part II. Stereochemistry of complexes of cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II), mercury(II), and palladium(II) and crystal structure analysis of the palladium complex","authors":"F. C. March, D. A. Couch, K. Emerson, J. Fergusson, W. Robinson","doi":"10.1039/J19710000440","DOIUrl":"https://doi.org/10.1039/J19710000440","url":null,"abstract":"Complexes have been formed between bivalent ions of cobalt, nickel, copper, zinc, mercury, and palladium and the the ligands 4,4′-dicarboxyethyl-3,3′,5,5′-tetramethyldipyrromethene (mpmH) and 3,4′-dicarboxyethyl-5-chloro-3′,4,5′-trimethyldipyrromethene (cpmH). The stereochemistry of these complexes has been investigated by measurement of magnetic susceptibility, and 1H n.m.r. spectra, and u.v. visible spectra. An X-ray determination of the crystal and molecular structure of the complex Pd(mpm)2 is reported. The palladium atom lies on a crystallographic centre of symmetry and is necessarily coplanar with the four co-ordinated nitrogen atoms of the ligand. The unique bidentate ligand is not planar.","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":"81446362","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: 26
Peroxo-complexes: triperoxovanadates(V) complexes 过氧配合物:三过氧钒酸盐(V)配合物
Pub Date : 1971-01-01 DOI: 10.1039/J19710001132
J. Sala-Pala, J. Guerchais
Triperoxovanadates of the type MI[V(O–O)3(AA)],nH2O and MI3[V(O–O)3(AA)′],H2O [M1= NH4, K or Na;(AA)= phen or bipy; (AA)′= C2O4(phen = 1,10-phenanthroline, bipy = 2,2′-bipyridyl)] have been prepared by reaction of the ligands with solutions of metavanadates in hydrogen peroxide. The molar conductivities of these salts in aqueous solution show the presence of 1 : 1 and 3 : 1 electrolytes. The existence, splitting, and shift of some i.r. bands including, in the 550–650 cm–1 region, bands assigned to the [graphic omitted] group show that the peroxophen, bipy and oxalato-groups are co-ordinated as bidentate ligands. U.v. spectra, magnetic susceptibilities, and an X-ray analysis are also reported. These complexes, in which the vanadium is probably eight-co-ordinate, are compared with the corresponding niobium and tantalum derivatives.
MI[V(O-O)3(AA)]、nH2O和MI3[V(O-O)3(AA) ']、H2O [M1= NH4、K或Na;(AA)= phen或bipy;(AA)′= C2O4(phen = 1,10-菲罗啉,bipy = 2,2′-联吡啶)]与偏胍酸盐溶液在过氧化氢中反应制备。这些盐在水溶液中的摩尔电导率表明存在1:1和3:1电解质。在550-650 cm-1的区域,一些红外波段的存在、分裂和移位,包括[图中省略的]基团的波段,表明过氧酚、bipy和草酸盐基团作为双齿配体进行配位。紫外光谱、磁化率和x射线分析也被报道。这些配合物,其中的钒可能是八坐标,与相应的铌和钽衍生物进行比较。
{"title":"Peroxo-complexes: triperoxovanadates(V) complexes","authors":"J. Sala-Pala, J. Guerchais","doi":"10.1039/J19710001132","DOIUrl":"https://doi.org/10.1039/J19710001132","url":null,"abstract":"Triperoxovanadates of the type MI[V(O–O)3(AA)],nH2O and MI3[V(O–O)3(AA)′],H2O [M1= NH4, K or Na;(AA)= phen or bipy; (AA)′= C2O4(phen = 1,10-phenanthroline, bipy = 2,2′-bipyridyl)] have been prepared by reaction of the ligands with solutions of metavanadates in hydrogen peroxide. The molar conductivities of these salts in aqueous solution show the presence of 1 : 1 and 3 : 1 electrolytes. The existence, splitting, and shift of some i.r. bands including, in the 550–650 cm–1 region, bands assigned to the [graphic omitted] group show that the peroxophen, bipy and oxalato-groups are co-ordinated as bidentate ligands. U.v. spectra, magnetic susceptibilities, and an X-ray analysis are also reported. These complexes, in which the vanadium is probably eight-co-ordinate, are compared with the corresponding niobium and tantalum 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":"81460333","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
Use and interpretation of non-rigorous force constants derived from C–O stretching frequencies of metal carbonyls. Part I. Symmetric carbonyls 由金属羰基的C-O拉伸频率导出的非严格力常数的使用和解释。第一部分对称羰基
Pub Date : 1971-01-01 DOI: 10.1039/J19710001885
J. Miller
Relationships are developed between non-rigorous C–O force constants and those of a quadratic general valence force field for metal carbonyls whose ligands are symmetry-equivalent. The equations are tested by reference to full calculations on MCO molecules and to data available for group VIA hexacarbonyls. Approximations involved give errors which are of the same order as experimental frequency errors. The associated normal co-ordinate treatment leads, as part of the same approximation, to the conclusion that non-rigorous force constants are valid and realistic quantities so long as the co-ordinate system is properly defined.
建立了配体对称等效的金属羰基的非严格C-O力常数与二次一般价力场的关系。通过参考MCO分子的完整计算和VIA基团六羰基的可用数据,对方程进行了测试。所涉及的近似误差与实验频率误差的数量级相同。相关的法向坐标处理,作为同一近似的一部分,得出的结论是,只要坐标系是正确定义的,非严格的力常数是有效的和现实的量。
{"title":"Use and interpretation of non-rigorous force constants derived from C–O stretching frequencies of metal carbonyls. Part I. Symmetric carbonyls","authors":"J. Miller","doi":"10.1039/J19710001885","DOIUrl":"https://doi.org/10.1039/J19710001885","url":null,"abstract":"Relationships are developed between non-rigorous C–O force constants and those of a quadratic general valence force field for metal carbonyls whose ligands are symmetry-equivalent. The equations are tested by reference to full calculations on MCO molecules and to data available for group VIA hexacarbonyls. Approximations involved give errors which are of the same order as experimental frequency errors. The associated normal co-ordinate treatment leads, as part of the same approximation, to the conclusion that non-rigorous force constants are valid and realistic quantities so long as the co-ordinate system is properly defined.","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":"81670330","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
期刊
Journal of The Chemical Society A: Inorganic, Physical, Theoretical
全部 Acc. Chem. Res. ACS Applied Bio Materials ACS Appl. Electron. Mater. ACS Appl. Energy Mater. ACS Appl. Mater. Interfaces ACS Appl. Nano Mater. ACS Appl. Polym. Mater. ACS BIOMATER-SCI ENG ACS Catal. ACS Cent. Sci. ACS Chem. Biol. ACS Chemical Health & Safety ACS Chem. Neurosci. ACS Comb. Sci. ACS Earth Space Chem. ACS Energy Lett. ACS Infect. Dis. ACS Macro Lett. ACS Mater. Lett. ACS Med. Chem. Lett. ACS Nano ACS Omega ACS Photonics ACS Sens. ACS Sustainable Chem. Eng. ACS Synth. Biol. Anal. Chem. BIOCHEMISTRY-US Bioconjugate Chem. BIOMACROMOLECULES Chem. Res. Toxicol. Chem. Rev. Chem. Mater. CRYST GROWTH DES ENERG FUEL Environ. Sci. Technol. Environ. Sci. Technol. Lett. Eur. J. Inorg. Chem. IND ENG CHEM RES Inorg. Chem. J. Agric. Food. Chem. J. Chem. Eng. Data J. Chem. Educ. J. Chem. Inf. Model. J. Chem. Theory Comput. J. Med. Chem. J. Nat. Prod. J PROTEOME RES J. Am. Chem. Soc. LANGMUIR MACROMOLECULES Mol. Pharmaceutics Nano Lett. Org. Lett. ORG PROCESS RES DEV ORGANOMETALLICS J. Org. Chem. J. Phys. Chem. J. Phys. Chem. A J. Phys. Chem. B J. Phys. Chem. C J. Phys. Chem. Lett. Analyst Anal. Methods Biomater. Sci. Catal. Sci. Technol. Chem. Commun. Chem. Soc. Rev. CHEM EDUC RES PRACT CRYSTENGCOMM Dalton Trans. Energy Environ. Sci. ENVIRON SCI-NANO ENVIRON SCI-PROC IMP ENVIRON SCI-WAT RES Faraday Discuss. Food Funct. Green Chem. Inorg. Chem. Front. Integr. Biol. J. Anal. At. Spectrom. J. Mater. Chem. A J. Mater. Chem. B J. Mater. Chem. C Lab Chip Mater. Chem. Front. Mater. Horiz. MEDCHEMCOMM Metallomics Mol. Biosyst. Mol. Syst. Des. Eng. Nanoscale Nanoscale Horiz. Nat. Prod. Rep. New J. Chem. Org. Biomol. Chem. Org. Chem. Front. PHOTOCH PHOTOBIO SCI PCCP Polym. Chem.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1