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1.
Coordinatively Unsaturated Diiron Complexes: Synthesis and Crystal Structures of [Fe2(CO)4(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] and [Fe2(CO)4(μ‐CH2)(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] [Fe2(μ‐CO)(CO)6(μ‐H)(μ‐PtBu2)] ( 1 ) reacts spontaneously with dppm (dppm = Ph2PCH2PPh2) to give [Fe2(μ‐CO)(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 2 c ). By thermolysis or photolysis, 2 c loses very easily one carbonyl ligand and yields the corresponding electronically and coordinatively unsaturated complex [Fe2(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 3 ). 3 exhibits a Fe–Fe double bond which could be confirmed by the addition of methylene to the corresponding dimetallacyclopropane [Fe2(CO)4(μ‐CH2)(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 4 ). The reaction of 1 with dppe (Ph2PC2H4PPh2) affords [Fe2(μ‐CO)(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppe)] ( 5 ). In contrast to the thermolysis of 2 c , yielding 3 , the heating of 5 in toluene leads rapidly to complete decomposition. The reaction of 1 with PPh3 yields [Fe2(CO)6(H)(μ‐PtBu2)(PPh3)] ( 6 a ), while with tBu2PH the compound [Fe2(μ‐CO)(CO)5(μ‐H)(μ‐PtBu2)(tBu2PH)] ( 6 b ) is formed. The thermolysis of 6 b affords [Fe2(CO)5(μ‐PtBu2)2] and the degradation products [Fe(CO)3(tBu2PH)2] and [Fe(CO)4(tBu2PH)]. The molecular structures of 3 , 4 and 6 b were determined by X‐ray crystal structure analyses. 相似文献
2.
Darstellung und Kristallstruktur eines Ditelluridovanadium(IV)‐Komplexes: [(μ‐η1‐Te2)(μ‐NtBu)2V2Cp2]
Synthesis and Crystal Structure of a Ditelluridovanadium(IV) Complex: [(μ‐η1‐Te2)(μ‐NtBu)2V2Cp2] [(μ‐η1‐Te2)(μ‐NtBu)2V2Cp2] ( 2 ) is formed from [tBuN = VCp(PMe3)2] ( 1 ) upon reaction with elemental tellurium. 1 and 2 are characterized by spectroscopic methods (MS; 1H, 13C, 51V NMR), in addition 2 by single crystal X‐ray diffraction. The crystal structure indicates a folded cyclodivanadazen ring bridged by a bidentated ditellurido ligand, the first example of this structure type. 相似文献
3.
Coordinatively Unsaturated Diruthenium Complexes: Synthesis and X‐ray Crystal Structures of [Ru2(CO)n(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] (n = 4; 5) and [Ru2(CO)4(μ‐CH2)(μ‐H)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] The reaction of [Ru2(μ‐CO)(CO)5(μ‐H)(μ‐PtBu2)(tBu2PH)] ( 2 ) with dppm yields the dinuclear species [Ru2(μ‐CO)(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 3 ) (dppm = Ph2PCH2PPh2). Under thermal or photolytic conditions 3 loses very easily one carbonyl ligand and affords the corresponding electronically and coordinatively unsaturated complex [Ru2(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 4 ). 4 is also obtainable by an one‐pot synthesis from [Ru3(CO)12], an excess of tBu2PH and stoichiometric amounts of dppm via the formation of [Ru2(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)2] ( 1 ). 4 exhibits a Ru–Ru double bond which could be confirmed by addition of methylene to the dimetallacyclopropane [Ru2(CO)4(μ‐CH2)(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 5 ). The molecular structures of 3 , 4 and 5 were determined by X‐ray crystal structure analyses. 相似文献
4.
Masahiro Nagaoka Hiroyuki Tsuruda Dr. Masa‐aki Amako Prof. Dr. Hiroharu Suzuki Prof. Dr. Toshiro Takao 《Angewandte Chemie (International ed. in English)》2015,54(49):14871-14874
A μ3‐η2:η2:η2‐silane complex, [(Cp*Ru)3(μ3‐η2:η2:η2‐H3SitBu)(μ‐H)3] ( 2 a ; Cp*=η5‐C5Me5), was synthesized from the reaction of [{Cp*Ru(μ‐H)}3(μ3‐H)2] ( 1 ) with tBuSiH3. Complex 2 a is the first example of a silane ligand adopting a μ3‐η2:η2:η2 coordination mode. This unprecedented coordination mode was established by NMR and IR spectroscopy as well as X‐ray diffraction analysis and supported by a density functional study. Variable‐temperature NMR analysis implied that 2 a equilibrates with a tautomeric μ3‐silyl complex ( 3 a ). Although 3 a was not isolated, the corresponding μ3‐silyl complex, [(Cp*Ru)3(μ3‐η2:η2‐H2SiPh)(H)(μ‐H)3] ( 3 b ), was obtained from the reaction of 1 with PhSiH3. Treatment of 2 a with PhSiH3 resulted in a silane exchange reaction, leading to the formation of 3 b accompanied by the elimination of tBuSiH3. This result indicates that the μ3‐silane complex can be regarded as an “arrested” intermediate for the oxidative addition/reductive elimination of a primary silane to a trinuclear site. 相似文献
5.
Hans‐Christian Bttcher Marion Graf Kurt Merzweiler Christoph Wagner 《无机化学与普通化学杂志》2000,626(6):1335-1340
Coordinatively Unsaturated Diruthenium Complexes: Synthesis and X‐ray Crystal Structures of [Ru2(CO)3L(μ‐η1 : η2‐C≡CPh)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] (L = CO, PnBu3) [Ru2(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 1 ) reacts with several phosphines (L) in refluxing toluene under substitution of one carbonyl ligand and yields the compounds [Ru2(CO)3L(μ‐H)(μ‐PtBu2)(μ‐dppm)] (L = PnBu3, 2 a ; L = PCy2H, 2 b ; L = dppm‐P, 2 c ; dppm = Ph2PCH2PPh2). The reactivity of 1 as well as the activated complexes 2 a – c towards phenylethyne was studied. Thus 1 , 2 a and 2 b , respectively, react with PhC≡CH in refluxing toluene with elimination of dihydrogen to the acetylide‐bridged complexes [Ru2(CO)4(μ‐η1 : η2‐C≡CPh)(μ‐PtBu2)(μ‐dppm)] ( 3 ) and [Ru2(CO)3L(μ‐η1 : η2‐C≡CPh)(μ‐PtBu2)(μ‐dppm)] ( 4 a and 4 b ). The molecular structures of 3 and 4 a were determined by crystal structure analyses. 相似文献
6.
Grald Lelais Peter Micuch Delphine Josien‐Lefebvre Francesco Rossi Dieter Seebach 《Helvetica chimica acta》2004,87(12):3131-3159
The Ser, Cys, and His side chains play decisive roles in the syntheses, structures, and functions of proteins and enzymes. For our structural and biomedical investigations of β‐peptides consisting of amino acids with proteinogenic side chains, we needed to have reliable preparative access to the title compounds. The two β3‐homoamino acid derivatives were obtained by Arndt–Eistert methodology from Boc‐His(Ts)‐OH and Fmoc‐Cys(PMB)‐OH (Schemes 2–4), with the side‐chain functional groups' reactivities requiring special precautions. The β2‐homoamino acids were prepared with the help of the chiral oxazolidinone auxiliary DIOZ by diastereoselective aldol additions of suitable Ti‐enolates to formaldehyde (generated in situ from trioxane) and subsequent functional‐group manipulations. These include OH→OtBu etherification (for β2hSer; Schemes 5 and 6), OH→STrt replacement (for β2hCys; Scheme 7), and CH2OH→CH2N3→CH2NH2 transformations (for β2hHis; Schemes 9–11). Including protection/deprotection/re‐protection reactions, it takes up to ten steps to obtain the enantiomerically pure target compounds from commercial precursors. Unsuccessful approaches, pitfalls, and optimization procedures are also discussed. The final products and the intermediate compounds are fully characterized by retention times (tR), melting points, optical rotations, HPLC on chiral columns, IR, 1H‐ and 13C‐NMR spectroscopy, mass spectrometry, elemental analyses, and (in some cases) by X‐ray crystal‐structure analysis. 相似文献
7.
Gary S. Nichol William Clegg 《Acta Crystallographica. Section C, Structural Chemistry》2011,67(1):o13-o17
The three title compounds were obtained by reactions which mimic, with more extreme conditions, the in vivo metabolism of barbiturates. 1‐(2‐Cyclohex‐2‐enylpropionyl)‐3‐methylurea, C11H18N2O2, (I), and 2‐ethylpentanamide, C8H17NO, (III), both crystallize with two unique molecules in the asymmetric unit; in the case of (III), one unique molecule exhibits whole‐molecule disorder. 2‐Ethyl‐5‐methylhexanamide, C9H19NO, (II), crystallizes as a fully ordered molecule with Z′ = 1. In the crystal structures, three different hydrogen‐bonding motifs are observed: in (I) a combination of R22(4) and R22(8) motifs, and in (II) and (III) a combination of R42(8) and R22(8) motifs. In all three structures, one‐dimensional ribbons are formed by N—H...O hydrogen‐bonding interactions. 相似文献
8.
The amino substituted bidentate chelating ligand 2‐amino‐5‐(2‐pyridyl)‐1,3,4‐thiadiazole (H2 L ) was used to prepare 3:1‐type coordination compounds of iron(II), cobalt(II) and nickel(II). In the iron(II) perchlorate complex [FeII(H2 L )3](ClO4)2·0.6MeOH·0.9H2O a 1:1 mixture of mer and fac isomers is present whereas [FeII(H2 L )3](BF4)2·MeOH·H2O, [CoII(H2 L )3](ClO4)2·2H2O and [NiII(H2 L )3](ClO4)2·MeOH·H2O feature merely mer derivatives. Moessbauer spectroscopy and variable temperature magnetic measurements revealed the [FeII(H2 L )3]2+ complex core to exist in the low‐spin state, whereas the [CoII(H2 L )3]2+ complex core resides in its high‐spin state, even at very low temperatures. 相似文献
9.
Sergey V. Krivovichev Elena V. Kir'yanova Stanislav K. Filatov Peter C. Burns 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(6):629-630
The monoclinic modification of dipotassium dichromate, β‐K2Cr2O7, has been synthesized in the K2Cr2O7–H2O system. The structure consists of K+ cations and Cr2O72? dimers. In contrast with triclinic α‐K2Cr2O7 [Kuz'min, Ilyukhin, Kharitonov & Belov (1969). Krist.Tech. 4 , 441–461], the Cr2O72? groups in β‐K2Cr2O7 have twofold crystallographic symmetry and are parallel to each other. 相似文献
10.
Gabriele Hierlmeier Dr. Alexander Hinz Prof. Dr. Robert Wolf Prof. Dr. Jose M. Goicoechea 《Angewandte Chemie (International ed. in English)》2018,57(2):431-436
The reactivity of two paramagnetic nickel(I) compounds, CpNi(NHC) (where Cp=cyclopentadienyl; NHC=1,3‐bis(2,4,6‐trimethylphenyl)imidazol‐2‐ylidene (IMes) or 1,3‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene (IPr)), towards [Na(dioxane)x][PnCO] (Pn=P, As) is described. These reactions afford symmetric bimetallic compounds (μ2:η2,η2‐Pn2){Ni(NHC)(CO)}2. Several novel intermediates en route to such species are identified and characterised, including a compound containing the PCO? anion in an unprecedented μ2:η2,η2‐binding mode. Ultimately, on treatment of the (μ2:η2,η2‐Pn2){Ni(IMes)(CO)}2 compounds with carbon monoxide, the Pn2 units can be released, affording P4 in the case of the phosphorus‐containing species, and elemental arsenic in the case of (μ2:η2,η2‐As2){Ni(IMes)(CO)}2. 相似文献
11.
Kenny Stahl Jette Oddershede Herbert Preikschat Erik Fischer Jacob S. Bennekou 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(3):m112-m115
The crystal structures of the title compounds, ammonium risedronate dihydrate, NH4+·C7H10NO7P2−·2H2O, (I), and potassium risedronate dihydrate, K+·C7H10NO7P2−·2H2O, (II), have been determined from single‐crystal X‐ray data collected at 120 K. Compound (I) forms a three‐dimensional hydrogen‐bonded network which connects the ammonium and risedronate ions and the water molecules. In compound (II), the K+ ions are seven‐coordinated in a capped distorted trigonal prism. The coordination polyhedra form chains by corner‐sharing, and these chains are connected by phosphonate groups into layers in the ac plane. The layers are stacked and connected by hydrogen bonds in the b direction. The risedronate conformation is determined by intramolecular interactions fine‐tuned by crystal packing effects. All H‐atom donors in both structures are involved in hydrogen bonding, with D⋯A distances between 2.510 (2) and 3.009 (2) Å. 相似文献
12.
Hans‐Christian Bttcher Marion Graf Kurt Merzweiler Christoph Wagner 《无机化学与普通化学杂志》2000,626(2):597-603
Coordinatively Unsaturated Diruthenium Complexes: Synthesis and X‐Ray Crystal Structures of [Ru2(CO)4(μ‐H)(μ‐S)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)], [Ru2(CO)4(μ‐X)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] (X = Cl, S2CH) [Ru2(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 1 ) reacts in benzene with elemental sulfur to the addition product [Ru2(CO)4(μ‐H)(μ‐S)(μ‐PtBu2)(μ‐dppm)] ( 2 ) (dppm = Ph2PCH2PPh2). 2 is also obtained by reaction of 1 with ethylene sulfide. The reaction of 1 with carbon disulfide yields with insertion of the CS2 into the Ru2(μ‐H) bridge the dithioformato complex [Ru2(CO)4(μ‐S2CH)(μ‐PtBu2)(μ‐dppm)] ( 3 ). Furthermore, 1 reacts with [NO][BF4] to the complex salt [Ru2(CO)4(μ‐NO)(μ‐H)(μ‐PtBu2)(μ‐dppm)][BF4] ( 4 ), and reaction of 1 with CCl4 or CHCl3 affords spontaneously [Ru2(CO)4(μ‐Cl)(μ‐PtBu2)(μ‐dppm)] ( 5 ) in nearly quantitative yield. The molecular structures of 2 , 3 and 5 were confirmed by crystal structure analyses. 相似文献
13.
Nilo Zanatta Elizandra C. S. Lopes Leonardo Fantinel Helio G. Bonacorso Marcos A. P. Martins 《Journal of heterocyclic chemistry》2002,39(5):943-947
The synthesis of a novel series of twelve 4‐(trihalomethyl)dipyrimidin‐2‐ylamines, from the cyclo‐condensation reaction of 4‐(trichloromethyl)‐2‐guanidinopyrimidine, with β‐alkoxyvinyl trihalomethyl ketones, of general formula: X3C‐C(O)‐C(R2)=C(R1)‐OR, where: X = F, Cl; R = Me, Et, ‐(CH2)2‐, ‐(CH2)3‐; R1 = H, Me; R2 = H, Me, ‐(CH2)2‐, ‐(CH2)3‐, is reported. The reactions were carried out in acetonitrile under reflux for 16 hours, leading to the dipyrimidin‐2‐ylamines in 65‐90% yield. Depending on the substituents of the vinyl ketone, tetrahydropyrimidines or aromatic pyrimidine rings were obtained from the cyclization reaction. When X = Cl, elimination of the trichloromethyl group was observed during the cyclization step. The structure of 4‐(trihalomethyl)dipyrimidin‐2‐ylamines was studied in detail by 1H‐, 13C‐ and 2D‐nmr spectroscopy. 相似文献
14.
Hans‐Christian Bttcher Marion Graf Kurt Merzweiler Christoph Wagner 《无机化学与普通化学杂志》2001,627(5):903-908
Heterobinuclear Complexes: Synthesis and X‐ray Crystal Structures of [RuRh(μ‐CO)(CO)4(μ‐PtBu2)(tBu2PH)], [RuRh(μ‐CO)(CO)3(μ‐PtBu2)(μ‐Ph2PCH2PPh2)], and [CoRh(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)] [Ru3Rh(CO)7(μ3‐H)(μ‐PtBu2)2(tBu2PH)(μ‐Cl)2] ( 2 ) yields by cluster degradation under CO pressure as main product the heterobinuclear complex [RuRh(μ‐CO)(CO)4(μ‐PtBu2)(tBu2PH)] ( 4 ). The compound crystallizes in the orthorhombic space group Pcab with a = 15.6802(15), b = 28.953(3), c = 11.8419(19) Å and V = 5376.2(11) Å3. The reaction of 4 with dppm (Ph2PCH2PPh2) in THF at room temperature affords in good yields [RuRh(μ‐CO)(CO)3(μ‐PtBu2)(μ‐dppm)] ( 7 ). 7 crystallizes in the triclinic space group P 1 with a = 9.7503(19), b = 13.399(3), c = 15.823(3) Å and V = 1854.6 Å3. Moreover single crystals of [CoRh(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)] ( 9 ) could be obtained and the single‐crystal X‐ray structure analysis revealed that 9 crystallizes in the monoclinic space group P21/a with a = 11.611(2), b = 13.333(2), c = 18.186(3) Å and V = 2693.0(8) Å3. 相似文献
15.
Gilles Wallez Sylvie Jaulmes Ammy Elfakir Jean‐Paul Souron Michel Quarton 《Acta Crystallographica. Section C, Structural Chemistry》2004,60(11):i107-i109
The ambient‐temperature form of dithallium sulfate, β‐Tl2SO4, is similar to β‐K2SO4 and is characterized by isolated sulfate tetrahedra and two different thallium sites with coordination numbers 9 and 11. All the atoms, except one O atom, lie on mirror planes. In spite of there being a high concentration of Tl+ cations, the stereochemical activity of the 6s2 pairs is low, similar to that of isotypic Tl2XO4 compounds (X = Cr and Se). This behaviour is the consequence of both weak Tl—O bonds and strong X—O bonds, because in a Tl—O—X linkage the electronic cloud of the O2− anion is strongly distorted and displaced towards X, resulting in a low negative charge in the face of the Tl atom. Consequently, the Coulombic repulsions between the lone pair and the O2− anions are weak. All of the Tl2XO4 compounds exhibit the same open packing of A+ cations and [XO4]2− anions as their isotypic alkali counterparts. 相似文献
16.
Li‐Fang Zhang Zhong‐Hai Ni Zhi‐Min Zong Xian‐Yong Wei Chun‐Hua Ge Hui‐Zhong Kou 《Acta Crystallographica. Section C, Structural Chemistry》2005,61(12):m542-m544
In the title one‐dimensional complex, {[MnIII(C9H10NO2)2]Cl}n, the Schiff base ligand 2‐[(2‐hydroxyethyl)iminomethyl]phenolate (Hsae−) functions as both a bridging and a chelating ligand. The MnIII ion is six‐coordinated by two N and four O atoms from four different Hsae− ligands, yielding a distorted MnO4N2 octahedral environment. Each [MnIII(Hsae)2]+ cationic unit has the Mn atom on an inversion centre and each [MnIII(Hsae)2]+ cation lies about another inversion centre. The chain‐like complex is further extended into a three‐dimensional network structure through Cl⋯H—O hydrogen bonds and C—H⋯π contacts involving the Hsae− rings. 相似文献
17.
Rafa Petrus Piotr Sobota 《Acta Crystallographica. Section C, Structural Chemistry》2012,68(10):m275-m280
The zinc alkoxide molecules in di‐μ3‐ethanolato‐diethyltetrakis(μ2‐2‐methyl‐4‐oxo‐4H‐pyran‐3‐olato‐κ3O3,O4:O3)tetrazinc(II), [Zn4(C2H5)2(C2H5O)2(C6H5O3)4], (I), and bis(μ3‐2‐ethoxyphenolato‐κ4O1,O2:O1:O1)bis(μ2‐2‐ethoxyphenolato‐κ3O1,O2:O1)bis(μ2‐2‐methyl‐4‐oxo‐4H‐pyran‐3‐olato‐κ3O3,O4:O3)bis(2‐methyl‐4‐oxo‐4H‐pyran‐3‐olato‐κ2O3,O4)tetrazinc(II) toluene disolvate, [Zn4(C6H5O3)4(C8H9O2)4]·2C7H8, (II), lie on crystallographic centres of inversion. The asymmetric units of (I) and (II) contain half of the tetrameric unit and additionally one molecule of toluene for (II). The ZnII atoms are four‐ and six‐coordinated in distorted tetrahedral and octahedral geometries for (I), and six‐coordinated in a distorted octahedral environment for (II). The ZnII atoms in both compounds are arranged in a defect dicubane Zn4O6 core structure composed of two EtZnO3 tetrahedra and ZnO6 octahedra for (I), and of four ZnO6 octahedra for (II), sharing common corners. The maltolate ligands exist mostly in a μ2‐bridging mode, while the guetholate ligands prefer a higher coordination mode and act as μ3‐ and μ2‐bridges. 相似文献
18.
Hans‐Christian Bttcher Marion Graf Kurt Merzweiler Christoph Wagner 《无机化学与普通化学杂志》2001,627(12):2657-2662
Activation of Carbon Disulfide on Triruthenium Clusters: Synthesis and X‐Ray Crystal Structure Analysis of [Ru3(CO)5(μ‐H)2(μ‐PCy2)(μ‐Ph2PCH2PPh2){μ‐η2‐PCy2C(S)}(μ3‐S)] and [Ru3(CO)5(CS)(μ‐H)(μ‐PtBu2)(μ‐PCy2)2(μ3‐S)] [Ru3(CO)6(μ‐H)2(μ‐PCy2)2(μ‐dppm)] ( 1 ) (dppm = Ph2PCH2PPh2) reacts under mild conditions with CS2 and yields by oxidative decarbonylation and insertion of CS into one phosphido bridge the opened 50 VE‐cluster [Ru3(CO)5(μ‐H)2(μ‐PCy2)(μ‐dppm){μ‐η2‐PCy2C(S)}(μ3‐S)] ( 2 ) with only two M–M bonds. The compound 2 crystallizes in the triclinic space group P 1 with a = 19.093(3), b = 12.2883(12), c = 20.098(3) Å; α = 84.65(3), β = 77.21(3), γ = 81.87(3)° and V = 2790.7(11) Å3. The reaction of [Ru3(CO)7(μ‐H)(μ‐PtBu2)(μ‐PCy2)2] ( 3 ) with CS2 in refluxing toluene affords the 50 VE‐cluster [Ru3(CO)5(CS)(μ‐H)(μ‐PtBu2)(μ‐PCy2)2(μ3‐S)] ( 4 ). The compound cristallizes in the monoclinic space group P 21/a with a = 19.093(3), b = 12.2883(12), c = 20.098(3) Å; β = 104.223(16)° and V = 4570.9(10) Å3. Although in the solid state structure one elongated Ru–Ru bond has been found the complex 4 can be considered by means of the 31P‐NMR data as an electron‐rich metal cluster. 相似文献
19.
Zilu Chen Huihui Xing Fupei Liang 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(12):m576-m578
In the title compound, [Mn(C5H2N2O4)(H2O)2]n, the MnII ion has a distorted octahedral geometry and the 4‐oxido‐2‐oxo‐1,2‐dihydropyrimidine‐5‐carboxylate (Hiso2−) anion acts as a μ3:η4‐bridging ligand. Two oxo O atoms from different Hiso2− ligands bridge two MnII ions, forming centrosymmetric dinuclear building blocks. Each dinuclear building block interacts with another four by the coordination of the oxide groups and carboxylate O atoms, producing a two‐dimensional framework in the ab plane. Hydrogen bonds further extend the two‐dimensional sheets into a three‐dimensional supramolecular framework. 相似文献
20.
Phosphonium Salts with Hydrogen Dihalide Anions HCl2?, HBr2?, HI2?, or HBrCl? Phosphonium hydrogen dihalides [R3PR′][XHY] (X = Y = Cl, Br, I; X = Br, Y = Cl) resp. [R3PH]HBr2 are obtained as extremely hydrolyzable crystals by reaction of phosphonium halides or tertiary phosphanes with hydrogen halide. According to IR spectroscopic results the solid compounds mostly contain anions [XHX]? with symmetric hydrogen bonds. In solution 1H NMR measurements show a slight (X = Cl, Br) or considerable (X = I) dissociation according to HX2? ? X? + HX. On heating the solid compounds decompose with formation of hydrogen halide and [R3PR′]X or [R3PH]X. In this process the hydrogen bromidechlorides [R3PR′][BrHCl] exclusively eliminate HCl. NMR studies (1H und 31P) with solutions containing [R3PH]HBr2 (R = phenyl, 1-naphtyl) or HBr and Ph3P in varying molar ratios show that a fast proton exchange between the competing Lewis bases R3P and Br? exists. 相似文献