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1.
Alexander Donchev Andreas Schnepf Elke Baum Gregor Stßer Hansgeorg Schnckel 《无机化学与普通化学杂志》2002,628(1):157-161
[Ga6R8]2– (R = SiPh2Me): A Metalloid Cluster Compound with an Unexpected Ga6‐Frame The reaction of a metastable solution of GaBr with a solution of LiSiPh2Me in a toluene/THF mixture results in orange coloured crystals of [Ga6(SiPh2Me)8]2– · 2 [Li(THF)4]+ ( 1 ). The unexpected structure of the planar Ga6 frame (C2h) could also be realized with the help of DFT calculation. DFT calculations furthermore show that 1 is energetically favoured against an octahedral Ga6R62– species and R2. In contrast calculations for the similar Al and B species show that in these cases the octahedral entities are favoured. These results demonstrate that even for similar compounds of B, Al, and Ga Wade rules are too general and that they cannot predict the correct structure. Moreover the atomic arrangement within 1 shows that a structure is preferred which is also present in allotropic β‐Ga and that therefore clusters of this type should be called metalloid or more general elementoid. 相似文献
2.
Neil M. Boag Kathleen M. Coward Anthony C. Jones Martyn E. Pemble J. Robin Thompson 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(12):1438-1439
The hydrolysis product [Ga2(C3H7)4(OH)2]·C14H32N4, derived from the tetrakis(triisopropylgallium)–1,4,8,11‐tetramethyl‐1,4,8,11‐tetraazacyclotetradecane (1/1) adduct, consists of a centrosymmetric [iPr2Ga(μ‐OH)]2 unit hydrogen bonded through the hydroxyl group to a nitrogen on an adjacent centrosymmetric 1,4,8,11‐tetramethyl‐1,4,8,11‐tetraazacyclotetradecane molecule, resulting in the generation of a molecular chain through the crystal. 相似文献
3.
Satoshi Matsunaga Yusuke Inoue Takuya Otaki Hironori Osada Kenji Nomiya 《无机化学与普通化学杂志》2016,642(7):539-545
Al‐ and Ga‐containing open‐Dawson polyoxometalates (POMs), K10[{Al4(μ‐OH)6}{α,α‐Si2W18O66}] · 28.5H2O ( Al4 ‐ open ) and K10[{Ga4(μ‐OH)6}(α,α‐Si2W18O66)] · 25H2O ( Ga4 ‐ open ) were synthesized by the reaction of trilacunary Keggin POM, [A‐α‐SiW9O34]10–, with Al(NO3)3 · 9H2O or Ga(NO3)3 · nH2O, and unequivocally characterized by single‐crystal X‐ray analysis, 29Si and 183W NMR, and FT‐IR spectroscopy as well as elemental analysis and TG/DTA. Single‐crystal X‐ray analysis revealed that the {M4(μ‐OH)6}6+ (M = Al, Ga) clusters were included in an open pocket of the open‐Dawson polyanion, [α,α‐Si2W18O66]16–, which was constituted by the fusion of two trilacunary Keggin POMs via two W–O–W bonds. These two open‐Dawson structural POMs showed clear difference of the bite angles depending on the size of ionic radii. In cases of both compounds, the solution 29Si and 183W NMR spectra in D2O showed only one signal and five signals, respectively. These spectra were consistent with the molecular structures of Al4 ‐ and Ga4 ‐ open , suggesting that these polyoxoanions were obtained as single species and maintained their molecular structures in solution. 相似文献
4.
Wei Liu Jing‐Lin Zuo Emmanuel Ngwang Nfor Xiao‐Zeng You Offiong Efanga Offiong 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(5):m211-m213
The title compound, [Zn2(C2H3O2)2(C8H9N4S)2], is a centrosymmetric dinuclear molecule with two acetate bridging ligands in a syn–syn arrangement. The ZnII atom is five‐coordinated in a trigonal–bipyramidal configuration by three thiosemicarbazone atoms (two N and one S) and by an O atom from each of the two acetate groups. 相似文献
5.
Univalent Gallium Complexes of Simple and ansa‐Arene Ligands: Effects on the Polymerization of Isobutylene
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Martin R. Lichtenthaler Steffen Maurer Robert J. Mangan Florian Stahl Florian Mönkemeyer Julian Hamann Prof. Dr. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):157-165
Using [Ga(C6H5F)2]+[Al(ORF)4]?( 1 ) (RF=C(CF3)3) as starting material, we isolated bis‐ and tris‐η6‐coordinated gallium(I) arene complex salts of p‐xylene (1,4‐Me2C6H4), hexamethylbenzene (C6Me6), diphenylethane (PhC2H4Ph), and m‐terphenyl (1,3‐Ph2C6H4): [Ga(1,4‐Me2C6H4)2.5]+ ( 2+ ), [Ga(C6Me6)2]+ ( 3+ ), [Ga(PhC2H4Ph)]+ ( 4+ ) and [(C6H5F)Ga(μ‐1,3‐Ph2C6H4)2Ga(C6H5F)]2+ ( 52+ ). 4+ is the first structurally characterized ansa‐like bent sandwich chelate of univalent gallium and 52+ the first binuclear gallium(I) complex without a Ga?Ga bond. Beyond confirming the structural findings by multinuclear NMR spectroscopic investigations and density functional calculations (RI‐BP86/SV(P) level), [Ga(PhC2H4Ph)]+[Al(ORF)4]?( 4 ) and [(C6H5F)Ga(μ‐1,3‐Ph2C6H4)2Ga(C6H5F)]2+{[Al(ORF)4] ?}2 ( 5 ), featuring ansa‐arene ligands, were tested as catalysts for the synthesis of highly reactive polyisobutylene (HR‐PIB). In comparison to the recently published 1 and the [Ga(1,3,5‐Me3C6H3)2]+[Al(ORF)4]? salt ( 6 ) (1,3,5‐Me3C6H3=mesitylene), 4 and 5 gave slightly reduced reactivities. This allowed for favorably increased polymerization temperatures of up to +15 °C, while yielding HR‐PIB with high contents of terminal olefinic double bonds (α‐contents=84–93 %), low molecular weights (Mn=1000–3000 g mol?1) and good monomer conversions (up to 83 % in two hours). While the chelate complexes delivered more favorable results than 1 and 6 , the reaction kinetics resembled and thus concurred with the recently proposed coordinative polymerization mechanism. 相似文献
6.
The Hexagallane [Ga6{SiMe(SiMe3)2}6] and the closo‐Hexagallanate [Ga6{Si(CMe3)3}4 (CH2C6H5)2]2— — the Transition to an Unusual precloso‐Cluster The closo hexagallanate [Ga6R4(CH2Ph)2]2— (R = SitBu3) as well as the hexagallane Ga6R6 (R = SiMe(SiMe3)2) with only six cluster electron pairs were isolated from reactions of “GaI” with the corresponding silanides. The structure of the latter is derived from an octahedron by a Jahn‐Teller‐distortion and is different from the capped trigonal bipyramidal one expected by the Wade‐Mingos rules. Both compounds were characterized by X‐ray crystallography. The bonding is discussed with simplified Ga6H6 and Ga6H62— models via DFT methods. 相似文献
7.
Tetrakis(p‐tolyl)oxalamidinato‐bis[acetylacetonatopalladium(II)] ([Pd2(acac)2(oxam)]) reacted with Li–C≡C–C6H5 in THF with formation of [Pd(C≡C–C6H5)4Li2(thf)4] ( 1a ). Reaction of [Pd2(acac)2(oxam)] with a mixture of 6 equiv. Li–C≡C–C6H5 and 2 equiv. LiCH3 resulted in the formation of [Pd(CH3)(C≡C–C6H5)3Li2(thf)4] ( 2 ), and the dimeric complex [Pd2(CH3)4(C≡C–C6H5)4Li4(thf)6] ( 3 ) was isolated upon reaction of [Pd2(acac)2(oxam)] with a mixture of 4 equiv. Li–C≡C–C6H5 and 4 equiv. LiCH3. 1 – 3 are extremely reactive compounds, which were isolated as white needles in good yields (60–90%). They were fully characterized by IR, 1H‐, 13C‐, 7Li‐NMR spectroscopy, and by X‐ray crystallography of single crystals. In these compounds Li ions are bonded to the two carbon atoms of the alkinyl ligand. 1a reacted with Pd(PPh3)4 in the presence of oxygen to form the already known complexes trans‐[Pd(C≡C–C6H5)2(PPh3)2] and [Pd(η2‐O2)(PPh3)2]. In addition, 1a is an active catalyst for the Heck coupling reaction, but less active in the catalytic Sonogashira reaction. 相似文献
8.
Alexandr V. Yatsenko Ksenia A. Paseshnichenko 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(5):493-497
The crystal structures of 2‐hydroxy‐5‐[(E)‐(4‐nitrophenyl)diazenyl]benzoic acid, C13H9N3O5, (I), ammonium 2‐hydroxy‐5‐[(E)‐phenyldiazenyl]benzoate, NH4+·C13H9N2O3−, (II), and sodium 2‐hydroxy‐5‐[(E)‐(4‐nitrophenyl)diazenyl]benzoate trihydrate, Na+·C13H8N3O5−·3H2O, (III), have been determined using single‐crystal X‐ray diffraction. In (I) and (III), the phenyldiazenyl and carboxylic acid/carboxylate groups are in an anti orientation with respect to each other, which is in accord with the results of density functional theory (DFT) calculations, whereas in (II), the anion adopts a syn conformation. In (I), molecules form slanted stacks along the [100] direction. In (II), anions form bilayers parallel to (010), the inner part of the bilayers being formed by the benzene rings, with the –OH and –COO− substituents on the bilayer surface. The NH4+ cations in (II) are located between the bilayers and are engaged in numerous N—H...O hydrogen bonds. In (III), anions form layers parallel to (001). Both Na+ cations have a distorted octahedral environment, with four octahedra edge‐shared by bridging water O atoms, forming [Na4(H2O)12]4+ units. 相似文献
9.
Peng‐Fei Cui Yang Gao Shu‐Ting Guo Yue‐Jian Lin Zhen‐Hua Li Guo‐Xin Jin 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(24):8213-8217
In this work, a pincer‐type complex [Cp*Ir‐(SNPh)(SNHPh)(C2B10H9)] ( 2 ) was synthesized and its reactivity studied in detail. Interestingly, molecular hydrogen can induce the transformation between the metalloradical [Cp*Ir‐(SNPh)2(C2B10H9)] ( 5 .) and 2 . A mixed‐valence complex, [(Cp*Ir)2‐(SNPh)2(C2B10H8)] ( 7 .+), was also synthesized by one‐electron oxidation. Studies show that 7 .+ is fully delocalized, possessing a four‐centered‐one‐electron (S‐Ir‐Ir‐S) bonding interaction. DFT calculations were also in good agreement with the experimental results. 相似文献
10.
Tatiana R. Amarante Isabel S. Gonalves Filipe A. Almeida Paz 《Acta Crystallographica. Section C, Structural Chemistry》2009,65(4):m168-m170
The reaction between fluorenyllithium and Mo(η3‐C3H5)Cl(NCMe)2(CO)2 led to the isolation of di‐μ3‐chlorido‐di‐μ3‐hydroxido‐tetrakis[(η3‐allyl)dicarbonylmolybdenum(II)]–9‐fluorenone–tetrahydrofuran (1/1/1), [Mo4(C3H5)4Cl2(OH)2(CO)8]·C4H8O·C13H8O. The tetrametallic Mo4 unit constitutes the first example of a complex containing simultaneously two μ3‐OH groups and two μ3‐Cl anions capping the metallic trigonal prism. The four crystallographically independent Mo2+ centres exhibit distorted octahedral geometry with the η3‐allyl groups being trans‐coordinated to a μ3‐OH group and the carbonyl groups occupying the equatorial plane. Space‐filling tetrahydrofuran and 9‐fluorenone molecules are engaged in strong O—H...O hydrogen‐bonding interactions with Mo4(η3‐allyl)4Cl2(OH)2(CO)8 complexes. 相似文献
11.
Jaromír Marek Zdenk Trvní
ek Pavel Kopel 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(11):m429-m431
The title compound, [Mn(C12H8N2)2(H2O)2](C4H4O4S)·[Mn(C4H4O4S)(C12H8N2)2]·13H2O, contains one dianion of thiodiglycolic acid (tdga2−) and two independent manganese(II) moieties, viz. [Mn(phen)2(H2O)2]2+ and [Mn(tdga)(phen)2], where phen is 1,10‐phenanthroline. The MnII atoms are octahedrally coordinated by four N atoms of two bidentate phen ligands [Mn—N = 2.240 (2)–2.3222 (19) Å] and either two water O atoms or two tdga carboxyl O atoms [Mn—O = 2.1214 (17)–2.1512 (17) Å]. The tdga ligand chelates as an O,O′‐bidentate ligand, forming an eight‐membered ring with one Mn atom. The free tdga2− dianion is hydrogen bonded to an [Mn(phen)2(H2O)2]2+ ion, with O⋯O distances of 2.606 (2) and 2.649 (2) Å. The crystal structure is further stabilized by an extensive network of hydrogen bonds involving 13 water molecules. 相似文献
12.
Maria V. Kashina Mikhail A. Kinzhalov Andrey S. Smirnov Daniil M. Ivanov Alexander S. Novikov Vadim Yu. Kukushkin 《化学:亚洲杂志》2019,14(21):3915-3920
The dihalomethanes CH2X2 (X=Cl, Br, I) were co‐crystallized with the isocyanide complexes trans‐[MXM2(CNC6H4‐4‐XC)2] (M=Pd, Pt; XM=Br, I; XC=F, Cl, Br) to give an extended series comprising 15 X‐ray structures of isostructural adducts featuring 1D metal‐involving hexagon‐like arrays. In these structures, CH2X2 behave as bent bifunctional XB/XB‐donating building blocks, whereas trans‐[MXM2(CNC6H4‐4‐XC)2] act as a linear XB/XB acceptors. Results of DFT calculations indicate that all XCH2–X???XM–M contacts are typical noncovalent interactions with estimated strengths in the range of 1.3–3.2 kcal mol?1. A CCDC search reveals that hexagon‐like arrays are rather common but previously overlooked structural motives for adducts of trans‐bis(halide) complexes and halomethanes. 相似文献
13.
Graham Smith Urs D. Wermuth 《Acta Crystallographica. Section C, Structural Chemistry》2011,67(7):o259-o264
The structures of the 1:1 proton‐transfer compounds of isonipecotamide (piperidine‐4‐carboxamide) with 4‐nitrophthalic acid [4‐carbamoylpiperidinium 2‐carboxy‐4‐nitrobenzoate, C6H13N2O8+·C8H4O6−, (I)], 4,5‐dichlorophthalic acid [4‐carbamoylpiperidinium 2‐carboxy‐4,5‐dichlorobenzoate, C6H13N2O8+·C8H3Cl2O4−, (II)] and 5‐nitroisophthalic acid [4‐carbamoylpiperidinium 3‐carboxy‐5‐nitrobenzoate, C6H13N2O8+·C8H4O6−, (III)], as well as the 2:1 compound with terephthalic acid [bis(4‐carbamoylpiperidinium) benzene‐1,2‐dicarboxylate dihydrate, 2C6H13N2O8+·C8H4O42−·2H2O, (IV)], have been determined at 200 K. All salts form hydrogen‐bonded structures, viz. one‐dimensional in (II) and three‐dimensional in (I), (III) and (IV). In (I) and (III), the centrosymmetric R22(8) cyclic amide–amide association is found, while in (IV) several different types of water‐bridged cyclic associations are present [graph sets R42(8), R43(10), R44(12), R33(18) and R64(22)]. The one‐dimensional structure of (I) features the common `planar' hydrogen 4,5‐dichlorophthalate anion, together with enlarged cyclic R33(13) and R43(17) associations. In the structures of (I) and (III), the presence of head‐to‐tail hydrogen phthalate chain substructures is found. In (IV), head‐to‐tail primary cation–anion associations are extended longitudinally into chains through the water‐bridged cation associations, and laterally by piperidinium–carboxylate N—H...O and water–carboxylate O—H...O hydrogen bonds. The structures reported here further demonstrate the utility of the isonipecotamide cation as a synthon for the generation of stable hydrogen‐bonded structures. An additional example of cation–anion association with this cation is also shown in the asymmetric three‐centre piperidinium–carboxylate N—H...O,O′ interaction in the first‐reported structure of a 2:1 isonipecotamide–carboxylate salt. 相似文献
14.
Viktor A. Tafeenko Gennady N. Panin Andrey N. Baranov Ivan N. Bardasov Leonid A. Aslanov 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(12):m541-m547
Yellow–orange tetraaquabis(3‐cyano‐4‐dicyanomethylene‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olato‐κN3)cadmium(II) dihydrate, [Cd(C8HN4O2)2(H2O)4]·2H2O, (I), and yellow tetraaquabis(3‐cyano‐4‐dicyanomethylene‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olato‐κN3)cadmium(II) 1,4‐dioxane solvate, [Cd(C8HN4O2)2(H2O)4]·C4H8O2, (II), contain centrosymmetric mononuclear Cd2+ coordination complex molecules in different conformations. Dark‐red poly[[decaaquabis(μ2‐3‐cyano‐4‐dicyanomethylene‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olato‐κ2N:N′)bis(μ2‐3‐cyano‐4‐dicyanomethylene‐1H‐pyrrole‐2,5‐diolato‐κ2N:N′)tricadmium] hemihydrate], [Cd3(C8HN4O2)2(C8N4O2)2(H2O)10]·0.5H2O, (III), has a polymeric two‐dimensional structure, the building block of which includes two cadmium cations (one of them located on an inversion centre), and both singly and doubly charged anions. The cathodoluminescence spectra of the crystals are different and cover the wavelength range from UV to red, with emission peaks at 377 and 620 nm for (III), and at 583 and 580 nm for (I) and (II), respectively. 相似文献
15.
Zoran D. Tomi
eljko K. Jaimovi Vukadin M. Leovac Valeria I. eljevi 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(7):777-779
The title compound, bis(μ‐4‐acetyl‐3‐amino‐5‐methylpyrazolato‐N1:N2)bis[(acetato‐O)(4‐acetyl‐3‐amino‐5‐methylpyrazole‐N2)zinc(II)], [Zn2(C6H8N3O)2(C2H3O2)2(C6H9N3O)2], ex‐ists as a centrosymmetric binuclear molecule with two tetrahedrally coordinated Zn atoms bridged by two pyrazolate anions. The geometry of the terminal and bridging pyrazole ligands are slightly different as a consequence of their differing modes of coordination. 相似文献
16.
Alkali‐Metal Trichloroacetates for Dichloromethylenation of Fullerenes: Nucleophilic Addition‐Substitution Route
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Marina G. Apenova Vladimir A. Akhmetov Nikita M. Belov Dr. Alexey A. Goryunkov Dr. Ilya N. Ioffe Dr. Natalia S. Lukonina Dr. Vitaliy Yu. Markov Prof. Dr. Lev N. Sidorov 《化学:亚洲杂志》2014,9(3):915-923
The first experimental evidence that fullerenes react with alkali‐metal trichloroacetates through a nucleophilic addition‐substitution route, yielding dichloromethylenefullerenes as the final products, is reported. The intermediates, C60(CCl3)? and C70(CCl3)? anions, have been isolated in their protonated forms as ortho‐C60(CCl3)H, as well as three ortho and one para isomer of C70(CCl3)H. The structures were unambiguously determined by means of 1H, 13C, and 1H–13C HMBC NMR spectroscopy along with UV/Vis spectroscopy. The observed regiochemistry was analyzed with the aid of quantum chemical calculations. Conversion of the protonated compounds into the [6,6]‐closed C60/70(CCl2) cycloadducts under basic conditions can be effected only for the ortho isomers, whereas para‐C70(CCl3)H decomposes back into pristine C70. 相似文献
17.
Five new copper chalcogenide cluster molecules, [Cu4(S–C6H4–Br)4(PPh3)4] ( 1 ), [Cu22Se6(S–C6H4–Br)10(PPh3)8] ( 2 ), [Cu28Se6(S–C6H4–Br)16(PPh3)8] ( 3 ), [Cu47Se10(S–C6H4–Br)21(OAc)6(PPh3)8] ( 4 ) and [Cu8(S–C6H4–Br)6(S2C–NMe2)2(PPh3)4] ( 5 ) have been synthesized and characterized by single‐crystal X‐ray structure analysis. Compounds 1 – 4 were prepared from the reaction of CuOAc, p‐Br–C6H4–SSiMe3 and Se(SiMe3)2 in the presence of PPh3. In a further reaction of 1 with iPrMgCl and (Me2N–CS2)2 cluster 5 was crystallized. 相似文献
18.
l‐Alanyl‐glutamine dipeptide assembles with CuII ions to give the 2D coordination framework [Cu2(C8H13N3O4)2·2H2O]n ( 1 ) in which amino acid residues result in specific void space. In presence of 4,4′‐bipyridine, framework 1 is turned into a binuclear complex [Cu2(C8H13N3O4)2(H2O)2(C10H8N2)·8H2O] ( 2 ), which is further linked into a 2D hydrogen‐bonded layer in which amino acid residues induce a hydrogen‐bonded water cluster containing eight water molecules in the void space. 相似文献
19.
Igor V. Kazakov Michael Bodensteiner Alexey Y. Timoshkin 《Acta Crystallographica. Section C, Structural Chemistry》2014,70(3):312-314
The molecular structures of trichlorido(2,2′:6′,2′′‐terpyridine‐κ3N,N′,N′′)gallium(III), [GaCl3(C15H11N3)], and tribromido(2,2′:6′,2′′‐terpyridine‐κ3N,N′,N′′)gallium(III), [GaBr3(C15H11N3)], are isostructural, with the GaIII atom displaying an octahedral geometry. It is shown that the Ga—N distances in the two complexes are the same within experimental error, in contrast to expected bond lengthening in the bromide complex due to the lower Lewis acidity of GaBr3. Thus, masking of the Lewis acidity trends in the solid state is observed not only for complexes of group 13 metal halides with monodentate ligands but for complexes with the polydentate 2,2′:6′,2′′‐terpyridine donor as well. 相似文献
20.
Computational data for the tetragallium clusters K2Ga4(C6H3-2,6-Trip2)2 and Na2Ga4Trip6 (Trip=C6H2-2,4,6-i-Pr3) showed that significant Ga–Ga multiple bonding exists only in the latter species. The data for the M2Ga4R2 (M=Li, Na or K; R=H, Me or Ph) models of K2Ga4(C6H3-2,6-Trip2)2, which has a distorted octahedral K2Ga4 core structure incorporating an almost square Ga4 moiety, showed that they have an occupied bonding -orbital that is delocalized over the four galliums, thereby conferring formal aromatic character by the [4n+2] Hückel rule. However, the Ga–Ga bond order is approximately one, and the hypothetical free [Ga4H2]2– dianion is unstable toward electron dissociation. For the cluster Na2Ga4Trip6, calculations for the model compounds Ga4H6 and [Ga4H6]2–, which involve a central gallium trigonally substituted by three GaH2 units, confirmed that no multiple bonding exists in the neutral species Ga4H6 but that, upon reduction to [Ga4H6]2–, a -bond is formed which is delocalized over the Ga4 unit. The Ga–Ga distances that were calculated for all model species listed above are longer than those experimentally observed. This was attributed to the absence of alkali metal-aryl interactions in the model species. 相似文献