Thomas Rüther, K. Cavell, Nathalie Braussaud, B. Skelton, Allan H. White
The syntheses and characterisation of tri- and bi-dentate coordinated chromium(III) and vanadium(III) complexes of the general composition [MCl3(N⁁D⁁N)], [MCl3(N⁁N)]2 {M = Cr, (N⁁D⁁N) = (mim)3COCH32a [mim = 1-methylimidazolyl], (mim)2CHCH2PPh22b, (mim)2CHCH2C(O)But2c, (tBupim)3P 2d [tBupim = 1-isopropyl-4-tert-butylimidazolyl], (N⁁N) = (mim)2CH23e, (mim)2CH2PPh23f, (mim)2CO 3g, (Bzmim)2CO 3h [Bzmim = 1-methybenzimidazolyl], (tBupim)2CO 3i, (mim)2CNPh 3j; M = V: (N⁁D⁁N) = (mim)3COCH35a; (N⁁N) = (mim)2CO 5g}, [CrCl3(mim)3] 4k, and [CrCl3(MeTAM)] 6 (MeTAM = 1-methyltriacetylmethane) is described. Crystallisation of 3g from CH3CN/Et2O gave the mononuclear complex [CrCl3{(mim)2CO}(CH3CN)] 3g′. The molecular structure of 3g′ shows the chromium atom is quasi-octahedral, six-coordinate, the three coordinated chlorine atoms disposed mer in the coordination sphere. The electronic spectra of the chromium complexes exhibit d–d transitions typical of a pseudo-octahedral coordinated d3 ion, falling into the region ν14A2g → 4T2g 600–700 nm and ν24A2g → 4T1g(F) 430–470 nm, and 10Dq values between 14 400 and 16 700 cm−1. In the presence of MMAO the complexes give active catalyst systems for the conversion of ethylene into 1-alkenes or polymers, with activities and selectivities depending on the electronic and steric factors of the ligand system and the metal centre, respectively.
{"title":"Synthesis, characterisation and catalytic behaviour of a novel class of chromium(III) and vanadium(III) complexes containing bi- and tri-dentate imidazole chelating ligands: a comparative study","authors":"Thomas Rüther, K. Cavell, Nathalie Braussaud, B. Skelton, Allan H. White","doi":"10.1039/B207248C","DOIUrl":"https://doi.org/10.1039/B207248C","url":null,"abstract":"The syntheses and characterisation of tri- and bi-dentate coordinated chromium(III) and vanadium(III) complexes of the general composition [MCl3(N⁁D⁁N)], [MCl3(N⁁N)]2 \u0000{M = Cr, (N⁁D⁁N) \u0000= \u0000(mim)3COCH32a \u0000[mim = 1-methylimidazolyl], (mim)2CHCH2PPh22b, (mim)2CHCH2C(O)But2c, (tBupim)3P 2d \u0000[tBupim = 1-isopropyl-4-tert-butylimidazolyl], (N⁁N) \u0000= \u0000(mim)2CH23e, (mim)2CH2PPh23f, (mim)2CO 3g, (Bzmim)2CO 3h \u0000[Bzmim = 1-methybenzimidazolyl], (tBupim)2CO 3i, (mim)2CNPh 3j; M = V: (N⁁D⁁N) \u0000= \u0000(mim)3COCH35a; (N⁁N) \u0000= \u0000(mim)2CO 5g}, [CrCl3(mim)3] \u00004k, and [CrCl3(MeTAM)] \u00006 \u0000(MeTAM = 1-methyltriacetylmethane) is described. Crystallisation of 3g from CH3CN/Et2O gave the mononuclear complex [CrCl3{(mim)2CO}(CH3CN)] \u00003g′. The molecular structure of 3g′ shows the chromium atom is quasi-octahedral, six-coordinate, the three coordinated chlorine atoms disposed mer in the coordination sphere. The electronic spectra of the chromium complexes exhibit d–d transitions typical of a pseudo-octahedral coordinated d3 ion, falling into the region ν14A2g \u0000→ \u00004T2g 600–700 nm and ν24A2g \u0000→ \u00004T1g(F) 430–470 nm, and 10Dq values between 14 400 and 16 700 cm−1. In the presence of MMAO the complexes give active catalyst systems for the conversion of ethylene into 1-alkenes or polymers, with activities and selectivities depending on the electronic and steric factors of the ligand system and the metal centre, respectively.","PeriodicalId":17317,"journal":{"name":"Journal of The Chemical Society-dalton Transactions","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75268700","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}
Bis(2-hydroxy-1-naphthyl)methane reacts with chlorodiphenylphosphine to afford the bis(phosphinite), Ph2P{(–OC10H6)(μ-CH2)(C10H6O–)}PPh2 (1) in good yield. The bis(phosphinite) 1 reacts with elemental sulfur or selenium to give the corresponding disulfide or diselenide; the structure of the selenium derivative, Ph2P(Se){(–OC10H6)(μ-CH2)(C10H6O–)}P(Se)Ph2 (3) is confirmed by X-ray crystal structure analysis. Treatment of the ligand 1 with platinum metal derivatives results in the formation of ten-membered chelate complexes with the ligand showing an η2-mode of coordination. The elucidation of the structures of the products is based on NMR (1H and 31P) spectroscopic data. Molecular structures of [CpRuCl{η2-Ph2P{(–OC10H6)(μ-CH2)(C10H6O–)}PPh2-κP,κP}] (4) and [PtCl2{η2-Ph2P{(–OC10H6)(μ-CH2)(C10H6O–)}PPh2-κP,κP}] (7) are determined by single crystal X-ray studies.
{"title":"Synthesis and derivatization, structures and transition metal chemistry of a new large bite bis(phosphinite) derived from bis(2-hydroxy-1-naphthyl)methane","authors":"M. Balakrishna, R. Panda, J. Mague","doi":"10.1039/B206994F","DOIUrl":"https://doi.org/10.1039/B206994F","url":null,"abstract":"Bis(2-hydroxy-1-naphthyl)methane reacts with chlorodiphenylphosphine to afford the bis(phosphinite), Ph2P{(–OC10H6)(μ-CH2)(C10H6O–)}PPh2 \u0000(1) in good yield. The bis(phosphinite) \u00001 reacts with elemental sulfur or selenium to give the corresponding disulfide or diselenide; the structure of the selenium derivative, Ph2P(Se){(–OC10H6)(μ-CH2)(C10H6O–)}P(Se)Ph2 \u0000(3) is confirmed by X-ray crystal structure analysis. Treatment of the ligand 1 with platinum metal derivatives results in the formation of ten-membered chelate complexes with the ligand showing an η2-mode of coordination. The elucidation of the structures of the products is based on NMR (1H and 31P) spectroscopic data. Molecular structures of [CpRuCl{η2-Ph2P{(–OC10H6)(μ-CH2)(C10H6O–)}PPh2-κP,κP}] \u0000(4) and [PtCl2{η2-Ph2P{(–OC10H6)(μ-CH2)(C10H6O–)}PPh2-κP,κP}] \u0000(7) are determined by single crystal X-ray studies.","PeriodicalId":17317,"journal":{"name":"Journal of The Chemical Society-dalton Transactions","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90627039","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}
P. Hitchcock, D. A. Handley, Ting Huei Lee, G. Leigh
The diamine Me2NCH2NMe2 (tmmn) is capable of forming simple adducts with most metal(II) ions of the first transition series, but with nickel and cobalt a variety of additional products can be obtained from its reaction with the dihalides. The diamine may be monodentate or bidentate, it may (formally) lose a hydride to generate a cation, and each N–C bond may break, generating new products containing additional methyl groups or the ions (Me2NH2)+ or (Me2NCH2)+.
{"title":"Anomalous reactions of the diamine Me2NCH2NMe2 with nickel(II) and cobalt(II)","authors":"P. Hitchcock, D. A. Handley, Ting Huei Lee, G. Leigh","doi":"10.1039/B207818J","DOIUrl":"https://doi.org/10.1039/B207818J","url":null,"abstract":"The diamine Me2NCH2NMe2 \u0000(tmmn) is capable of forming simple adducts with most metal(II) ions of the first transition series, but with nickel and cobalt a variety of additional products can be obtained from its reaction with the dihalides. The diamine may be monodentate or bidentate, it may (formally) lose a hydride to generate a cation, and each N–C bond may break, generating new products containing additional methyl groups or the ions (Me2NH2)+ or (Me2NCH2)+.","PeriodicalId":17317,"journal":{"name":"Journal of The Chemical Society-dalton Transactions","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84436102","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 amphiphilic 5,11,17,23-tetrakis(1,1,3,3-tetramethylbutyl)-25,26,27,28-tetra(carboxymethoxy)calix[4]arene, 1, forms stable monolayers at the air–water interface which can be employed as supramolecular templates for induced calcite crystallization. Uniform, (012) oriented CaCO3 (calcite) single crystals grow underneath monolayers of 1 at low compression (π = 0.1–0.5 mN m−1), while more randomly oriented single crystals are obtained at higher surface pressure (π = 5–20 mN m−1). The use of easy-to-synthesize calixarenes for this particular area of crystal engineering is reported here for the first time. A range of structural analysis methods is employed in order to obtain a refined picture of the structural factors that govern the growth of uniformly oriented calcite crystals underneath monolayers of 1. Thus, the crystal structures of 5,11,17,23-tetrakis(1,1,3,3-tetramethylbutyl)-25,26,27,28-tetra(carboxymethoxy)calix[4]arene, 1, as well as of its Ca salt, 2, were solved and analysed in terms of typical supramolecular packing arrangements and coordination motifs. The Langmuir isotherms point to a liquid-condensed state of the monolayers of 1 throughout the investigated compression range. Brewster angle microscopic observation of the monolayer morphology at low surface pressure reveals a highly viscous consistency, which does not change upon further compression. Grazing incidence X-ray diffraction (GIXD) investigations on the monolayer structure provide no indications for the occurrence of a two-dimensional lattice of the alkyl chains. Considering the non-crystalline, highly dynamic state of the monolayer during crystal maturation, an epitaxial correlation based on geometric matching of lattice positions between the monolayer and the overgrowing calcite crystals is ruled out. We, therefore, suggest that non-specific monolayer properties such as average charge density or mean dipole moment are the main determinants for templated calcite growth in the present and related cases.
{"title":"Crystallization of (012) oriented calcite single crystals underneath monolayers of tetra(carboxymethoxy)calix[4]arenes","authors":"D. Volkmer, M. Fricke, D. Vollhardt, S. Siegel","doi":"10.1039/B206912A","DOIUrl":"https://doi.org/10.1039/B206912A","url":null,"abstract":"The amphiphilic 5,11,17,23-tetrakis(1,1,3,3-tetramethylbutyl)-25,26,27,28-tetra(carboxymethoxy)calix[4]arene, 1, forms stable monolayers at the air–water interface which can be employed as supramolecular templates for induced calcite crystallization. Uniform, (012) oriented CaCO3 \u0000(calcite) single crystals grow underneath monolayers of 1 at low compression (π \u0000= 0.1–0.5 mN m−1), while more randomly oriented single crystals are obtained at higher surface pressure (π \u0000= 5–20 mN m−1). The use of easy-to-synthesize calixarenes for this particular area of crystal engineering is reported here for the first time. A range of structural analysis methods is employed in order to obtain a refined picture of the structural factors that govern the growth of uniformly oriented calcite crystals underneath monolayers of 1. Thus, the crystal structures of 5,11,17,23-tetrakis(1,1,3,3-tetramethylbutyl)-25,26,27,28-tetra(carboxymethoxy)calix[4]arene, 1, as well as of its Ca salt, 2, were solved and analysed in terms of typical supramolecular packing arrangements and coordination motifs. The Langmuir isotherms point to a liquid-condensed state of the monolayers of 1 throughout the investigated compression range. Brewster angle microscopic observation of the monolayer morphology at low surface pressure reveals a highly viscous consistency, which does not change upon further compression. Grazing incidence X-ray diffraction (GIXD) investigations on the monolayer structure provide no indications for the occurrence of a two-dimensional lattice of the alkyl chains. Considering the non-crystalline, highly dynamic state of the monolayer during crystal maturation, an epitaxial correlation based on geometric matching of lattice positions between the monolayer and the overgrowing calcite crystals is ruled out. We, therefore, suggest that non-specific monolayer properties such as average charge density or mean dipole moment are the main determinants for templated calcite growth in the present and related cases.","PeriodicalId":17317,"journal":{"name":"Journal of The Chemical Society-dalton Transactions","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83404528","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 diphosphonic acid, N,N′-dimethyl-N,N′-ethylenediamine-bis(methylenephosphonic acid) (H4L) 1, along with its Ni(II) and Pb(II) complexes, have been synthesized and structurally determined. The structure of the diphosphonic acid features a 2D layer built from the molecular units interconnected by hydrogen bonds between phosphonate oxygen atoms and/or nitrogen atoms. Upon complexing with the Ni(II) ion, the diphosphonic acid acts as a tetradentate chelating ligand (2N, 2O), forming Ni(H2L)(H2O)22 molecular units, such units are also interconnected into a hydrogen bonded double layer via hydrogen bonds between uncoordinated phosphonate oxygen atoms. The ligand in Pb(H2L) 3 also chelates with a Pb(II) ion tetradentately, however, neighboring Pb(H2L) units are interconnected into a one-dimensional chain along the c-axis by a pair of μ2-chelating and bridging phosphonate oxygen atoms. Such chains are further interconnected into a 3D network via hydrogen bonds between uncoordinated phosphonate oxygen atoms. These structures demonstrate the important role of hydrogen bonds in the chemistry of divalent metal phosphonates.
{"title":"Building layered structures from hydrogen bonded molecular units and 1D metal phosphonate chains: synthesis, characterization and crystal structures of N,N′-dimethyl-N,N′-ethylenediamine-bis(methylenephosphonic acid), its Ni(II) and Pb(II) complexes","authors":"J. Mao, Zhike Wang, A. Clearfield","doi":"10.1039/B206343N","DOIUrl":"https://doi.org/10.1039/B206343N","url":null,"abstract":"The diphosphonic acid, N,N′-dimethyl-N,N′-ethylenediamine-bis(methylenephosphonic acid) \u0000(H4L) \u00001, along with its Ni(II) and Pb(II) complexes, have been synthesized and structurally determined. The structure of the diphosphonic acid features a 2D layer built from the molecular units interconnected by hydrogen bonds between phosphonate oxygen atoms and/or nitrogen atoms. Upon complexing with the Ni(II) ion, the diphosphonic acid acts as a tetradentate chelating ligand (2N, 2O), forming Ni(H2L)(H2O)22 molecular units, such units are also interconnected into a hydrogen bonded double layer via hydrogen bonds between uncoordinated phosphonate oxygen atoms. The ligand in Pb(H2L) \u00003 also chelates with a Pb(II) ion tetradentately, however, neighboring Pb(H2L) units are interconnected into a one-dimensional chain along the c-axis by a pair of μ2-chelating and bridging phosphonate oxygen atoms. Such chains are further interconnected into a 3D network via hydrogen bonds between uncoordinated phosphonate oxygen atoms. These structures demonstrate the important role of hydrogen bonds in the chemistry of divalent metal phosphonates.","PeriodicalId":17317,"journal":{"name":"Journal of The Chemical Society-dalton Transactions","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85837016","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}
S. Matsui, T. Spaniol, Yukihiro Takagi, Yasunori Yoshida, J. Okuda
A dibenzyl hafnium(IV) complex containing pyrrolide-imine chelate ligands was synthesized and investigated as an ethylene polymerisation catalyst.
合成了一种含吡咯烷-亚胺螯合配体的二苄基铪配合物，并对其作为乙烯聚合催化剂进行了研究。
{"title":"Efficient ethylene polymerisation catalysis by a cationic benzyl hafnium complex containing pyrrolide-imine ligands","authors":"S. Matsui, T. Spaniol, Yukihiro Takagi, Yasunori Yoshida, J. Okuda","doi":"10.1039/B209582C","DOIUrl":"https://doi.org/10.1039/B209582C","url":null,"abstract":"A dibenzyl hafnium(IV) complex containing pyrrolide-imine chelate ligands was synthesized and investigated as an ethylene polymerisation catalyst.","PeriodicalId":17317,"journal":{"name":"Journal of The Chemical Society-dalton Transactions","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83660689","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}
J. Aldrich-Wright, Ronald F. Fenton, I. Greguric, T. Hambley, Peter A. Williams
The conglomerate Δ,Λ-α-[Ru(picchxnMe2)(dpqC)](ClO4)2·0.5H2O and Λ-α-[Ru(S,S-picchxnMe2)(dpqC)](ClO4)2·0.5H2O (where picchxnMe2 = N,N′-dimethyl-1,2-di(2′-picolyl)-S,S-diaminocyclohexane and dpqC = dipyrido[3,2-a:2′3′-c](6,7,8,9-tetrahydro)phenazine) have been isolated. Single crystal X-ray structures have been determined, although it was discovered only after initial data had been collected that the Δ,Λ-α-[Ru(picchxnMe2)(dpqC)](ClO4)2·0.5H2O species was in fact a conglomerate. Λ-α-[Ru(S,S-picchxnMe2)(dpqC)](ClO4)2·0.5H2O crystallises in the orthorhombic space group C2221 with a = 15.127(2), b = 22.976(4), c = 25.561(7) A, (alternatively a = 15.187(3), b = 23.003(6), c = 25. 685(7) A, for the separate determination of a crystal of the conglomerate), Z = 8, and the Λ-α structure was refined to an R value of 0.059. This structure enables, for the first time, the correlation of the absolute configurations for Ru(II) complexes of the N4 tetradentate with their CD spectra. We also report here a procedure to synthesise and isolate enantiomerically pure isomers of tetradentate metal complexes of the types α- and β-[Ru(R*,R*-picchxnMe2)(dpqC)]2+.
分离得到了团聚体Δ，Λ-α-[Ru(picchxnMe2)(dpqC)](ClO4)2·0.5H2O和Λ-α-[Ru(S,S-picchxnMe2)(dpqC)](ClO4)2·0.5H2O(其中picchxnMe2 = N,N ' -二甲基-1,2-二(2 ' -吡啶基)-S,S-二氨基环己烷和dpqC =二吡啶[3,2-a:2 ' 3 ' -c](6,7,8,9-四氢)非那嗪)。单晶x射线结构已经确定，尽管在收集了初始数据后才发现Δ，Λ-α-[Ru(picchxnMe2)(dpqC)](ClO4)2·0.5H2O实际上是一个团岩。Λ-α-[Ru(S,S- picchxnme2)(dpqC)](ClO4) 2.0 h2o在正交空间群C2221中结晶，a = 15.127(2)， b = 22.976(4)， c = 25.561(7) a，(或a = 15.187(3)， b = 23.003(6)， c = 25)。685(7) A，单独测定砾岩晶体)，Z = 8， Λ-α结构细化至R值为0.059。该结构首次实现了N4四齿体Ru(II)配合物的绝对构型与其CD谱的相关性。本文还报道了一种合成和分离四齿金属配合物α-和β-[Ru(R*，R*- picchxnme2)(dpqC)]2+对映体纯异构体的方法。
{"title":"The stereospecific synthesis of Lambda-alpha-{dipyrido[3,2-a:2'3'-c](6,7,8,9-tetrahydro)phenazine[N,N'-di(2-picolyl)-2,5-dimethyl-2S,5S-diaminocyclohexane]ruthenium(II)} and related beta isomers","authors":"J. Aldrich-Wright, Ronald F. Fenton, I. Greguric, T. Hambley, Peter A. Williams","doi":"10.1039/B208369H","DOIUrl":"https://doi.org/10.1039/B208369H","url":null,"abstract":"The conglomerate Δ,Λ-α-[Ru(picchxnMe2)(dpqC)](ClO4)2·0.5H2O and Λ-α-[Ru(S,S-picchxnMe2)(dpqC)](ClO4)2·0.5H2O (where picchxnMe2 \u0000= \u0000N,N′-dimethyl-1,2-di(2′-picolyl)-S,S-diaminocyclohexane and dpqC = dipyrido[3,2-a:2′3′-c](6,7,8,9-tetrahydro)phenazine) have been isolated. Single crystal X-ray structures have been determined, although it was discovered only after initial data had been collected that the Δ,Λ-α-[Ru(picchxnMe2)(dpqC)](ClO4)2·0.5H2O species was in fact a conglomerate. Λ-α-[Ru(S,S-picchxnMe2)(dpqC)](ClO4)2·0.5H2O crystallises in the orthorhombic space group C2221 with a \u0000= 15.127(2), b \u0000= 22.976(4), c \u0000= 25.561(7) \u0000A, (alternatively a \u0000= 15.187(3), b \u0000= 23.003(6), c \u0000= 25. 685(7) \u0000A, for the separate determination of a crystal of the conglomerate), Z \u0000= 8, and the Λ-α structure was refined to an R value of 0.059. This structure enables, for the first time, the correlation of the absolute configurations for Ru(II) complexes of the N4 tetradentate with their CD spectra. We also report here a procedure to synthesise and isolate enantiomerically pure isomers of tetradentate metal complexes of the types α- and β-[Ru(R*,R*-picchxnMe2)(dpqC)]2+.","PeriodicalId":17317,"journal":{"name":"Journal of The Chemical Society-dalton Transactions","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74567408","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}
J. Bickley, A. Bond, Felipe García, Katja Jantos, Gavin T. Lawson, M. Mcpartlin, A. Steiner, D. Wright
The in situ reaction of the Sb(III) imido dimer [Me2NSb(µ-NCy)]2 with PhOH gives the tetrameric cubane [PhOSb(µ3-NCy)]4 (3). The analogous reaction of 2-pyOH (py = 2-pyridyl) gives the related Bi(III) cubane [pyOBi(µ3-NCy)]4 (4). The latter, which is a rare example of a structurally characterised Bi(III) imido compound, exhibits unusual molecular association of the tetrameric units in the solid state and fluxional behaviour in solution.
{"title":"Syntheses and structures of the cubanes [PhOSb(µ3-NCy)]4and [pyOBi(µ3-NCy)]4(Cy = cyclohexyl, py = 2-pyridyl)","authors":"J. Bickley, A. Bond, Felipe García, Katja Jantos, Gavin T. Lawson, M. Mcpartlin, A. Steiner, D. Wright","doi":"10.1039/B208302G","DOIUrl":"https://doi.org/10.1039/B208302G","url":null,"abstract":"The in situ reaction of the Sb(III) imido dimer [Me2NSb(µ-NCy)]2 with PhOH gives the tetrameric cubane [PhOSb(µ3-NCy)]4 \u0000(3). The analogous reaction of 2-pyOH (py = 2-pyridyl) gives the related Bi(III) cubane [pyOBi(µ3-NCy)]4 \u0000(4). The latter, which is a rare example of a structurally characterised Bi(III) imido compound, exhibits unusual molecular association of the tetrameric units in the solid state and fluxional behaviour in solution.","PeriodicalId":17317,"journal":{"name":"Journal of The Chemical Society-dalton Transactions","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"74737419","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}
J. Świątek-Kozłowska, E. Gumienna-Kontecka, Agnieszka Dobosz, Irina A. Golenya, I. Fritsky
Pyridine-2,6-dihydroxamic acid was found to be the most effective ligand for Ni2+ and Cu2+ ions among the known dihydroxamates. The stability constants of the title complexes are many orders of magnitude higher than those obtained for the other dihydroxamates. Only equimolar species are formed with Cu2+ ions, while NiL and bis-complexes are formed in the case of Ni2+. The [NiL2]2− complex anion contains compressed octahedral hexanitrogen surroundings of two meridionally coordinated ligands. The equatorial Ni–N(Py) bonds are significantly shorter than the axial Ni–N(hydroxamate) distances although the latter are formed by the deprotonated groups.
{"title":"Pyridine-2,6-dihydroxamic acid, a powerful dihydroxamate ligand for Ni2+ and Cu2+ ions","authors":"J. Świątek-Kozłowska, E. Gumienna-Kontecka, Agnieszka Dobosz, Irina A. Golenya, I. Fritsky","doi":"10.1039/B207271H","DOIUrl":"https://doi.org/10.1039/B207271H","url":null,"abstract":"Pyridine-2,6-dihydroxamic acid was found to be the most effective ligand for Ni2+ and Cu2+ ions among the known dihydroxamates. The stability constants of the title complexes are many orders of magnitude higher than those obtained for the other dihydroxamates. Only equimolar species are formed with Cu2+ ions, while NiL and bis-complexes are formed in the case of Ni2+. The [NiL2]2− complex anion contains compressed octahedral hexanitrogen surroundings of two meridionally coordinated ligands. The equatorial Ni–N(Py) bonds are significantly shorter than the axial Ni–N(hydroxamate) distances although the latter are formed by the deprotonated groups.","PeriodicalId":17317,"journal":{"name":"Journal of The Chemical Society-dalton Transactions","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80417974","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}
Hydrothermal reactions of mononuclear oxochloromolybdate(V) with oxalic acid in alcohol (methanol or 2-propanol) and pyridines (pyridine or 3-methylpyridine) media have afforded two polymeric compounds of molybdenum(V): N-methylpyridinum catena-μ-oxalato-O1,O2:O1′,O2′-(dichloro-di-μ-oxo-dioxodimolybdate(V)), (MeNC5H5)2n[Mo2O4(C2O4)Cl2]n1 and 3-methylpyridinium catena-μ-oxalato-O1,O2:O1′,O2′-(dichloro-di-μ-oxo-dioxodimolybdate(V)), (3-MePyH)2n[Mo2O4(C2O4)Cl2]n2. The compounds were fully characterized by X-ray structural analysis, infrared and NMR spectroscopy. The essentially isostructural anionic chains in 1and 2 are built of alternating pairs of {Mo2O4}2+ containing edge-sharing octahedra and planar oxalates giving a Mo ∶ oxalate ratio of 2. The bisbidentate oxalate acts as a bridge between two dinuclear subunits. The formation of a N-methylpyridinium cation from methanol and pyridine in the presence of molybdenum(V) and oxalic acid has not been documented before.
{"title":"The first oxalate-bridged one-dimensional polymer containing MoV2 dimers with single metal–metal bonds. Syntheses and structures of (MeNC5H5)2n[Mo2O4(C2O4)Cl2]n and (3-MePyH)2n[Mo2O4(C2O4)Cl2]n","authors":"B. Modec, J. V. Brenčič, D. Dolenc, J. Zubieta","doi":"10.1039/B207544J","DOIUrl":"https://doi.org/10.1039/B207544J","url":null,"abstract":"Hydrothermal reactions of mononuclear oxochloromolybdate(V) with oxalic acid in alcohol (methanol or 2-propanol) and pyridines (pyridine or 3-methylpyridine) media have afforded two polymeric compounds of molybdenum(V): N-methylpyridinum catena-μ-oxalato-O1,O2:O1′,O2′-(dichloro-di-μ-oxo-dioxodimolybdate(V)), (MeNC5H5)2n[Mo2O4(C2O4)Cl2]n1 and 3-methylpyridinium catena-μ-oxalato-O1,O2:O1′,O2′-(dichloro-di-μ-oxo-dioxodimolybdate(V)), (3-MePyH)2n[Mo2O4(C2O4)Cl2]n2. The compounds were fully characterized by X-ray structural analysis, infrared and NMR spectroscopy. The essentially isostructural anionic chains in 1and 2 are built of alternating pairs of {Mo2O4}2+ containing edge-sharing octahedra and planar oxalates giving a Mo ∶ oxalate ratio of 2. The bisbidentate oxalate acts as a bridge between two dinuclear subunits. The formation of a N-methylpyridinium cation from methanol and pyridine in the presence of molybdenum(V) and oxalic acid has not been documented before.","PeriodicalId":17317,"journal":{"name":"Journal of The Chemical Society-dalton Transactions","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2002-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88833388","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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