Synthesen und Reaktionen von Aluminiumalkoxid‐Verbindungen

Syntheses and Reactions of Aluminium Alkoxide Compounds Al(O^cHex)₃ ( 1 ) can be synthesized by the reaction of Al with cyclohexanol under evolving of H₂ in boiling xylene. [Li{Al(OCH₂Ph)₄}] ( 2 ) was obtained by treatment of PhCH₂OH with a 1 M solution of LiAlH₄ in THF. [{(THF)Li}₂{Al(O^tBu)₄}Cl] ( 3 ) is the result of the reaction of four equivalents of LiO^tBu on AlCl₃ in THF. 3 is the educt for the reactions with the Lewis‐acids InCl₃ and FeCl₃ in THF leading to the metalates [{(THF)₂Li}₂{Al(O^tBu)₄}] · [MCl₄] [M = In ( 4 ), Fe ( 5 )]. The attempt to react InCl₃ with four equivalents of LiO^tBu leads to only one isolated and characterized product, the complex [Li₄(O^tBu)₃(THF)₃Cl]₂ · THF ( 6 · THF), which can also be synthesized by the treatment of LiCl with three equivalents of LiO^tBu in THF. 1–6 · THF were characterized by NMR, IR and MS techniques as well as by X‐ray structure determinations. According to them, 1 , which is tetrameric in solution, is the first structurally characterized example of the proposed trimer form of aluminium alkoxides [ROAl{Al(OR)₄}₂] with a central trigonal bipyramidal coordinated Al atom. 2 forms a coordination polymer with a distorted tetrahedral coordination sphere of Li and Al, running along [100]. The trinuclear structure skeleton [{(THF)₂Li}₂{Al(O^tBu)₄}]⁺ is still present in the isotypical metalates 4 and 5 . The counter ions [MCl₄]^– possess nearly T_d symmetry. The remarkable structural motif of 6 · THF are two heterocubanes [Li₄(O^tBu)₃(THF)₃Cl] dimerized by Li–Cl bonds.     

CsF als Fluoridierungsmittel für Organometall-Verbindungen der Elemente der Gruppe 13

CsF as Fluoridation Agent for Organometal Compounds of the Elements of Group 13 Cs[i-Bu₃AlF] ( 1 ) can be obtained by the reaction of Al(i-Bu)₃ with CsF in toluene. In a halide exchange reaction of Mes*GaCl₂ with CsF in acetonitrile not the desired product Mes*GaF₂ (Mes* = 2,4,6-(t-Bu)₃C₆H₂) was isolated but the metalate Cs[Mes*GaF₃] ( 2 ), formed by the addition of a third unit CsF. A ligand distribution was observed by the treatment of [(PhCH₂)₂GaTe(t-Bu)]₂ with CsF in THF. The triorganofluoro gallate [Cs{(PhCH₂)₃GaF}]₂ ( 3 ) was isolated. The triorganofluoro gallate Cs[Me₃GaF] does not react with dry O₂ in THF. With S₈ in THF a reaction was achieved and the diorganodifluoro gallate [Cs(THF)_0,5(Me₂GaF₂)] ( 4 ) could be characterized. The treatment of MesInBr₂ with CsF in acetonitrile gives as only identified compound the indate Cs[MesInBr₃] ( 5 ).     

Sesquialkoxide von Gallium und Indium

Sesquialkoxides of Gallium and Indium Treatment of GaMe₃ with one equivalent of HO^cHex in toluene at 20 °C leads to [Me₂GaO^cHex]₂ ( 4 ) under evolution of methane. The reaction of InMe₃ with two equivalents of HO^cHex leads under similar conditions not to [MeIn(O^cHex)₂]_n but to the sesquialkoxide [In{Me₂In(O^cHex)₂}₃] ( 5 ). 5 can be described also as [{Me₂InO^cHex)}₂{MeIn(O^cHex)₂}₂]. The use of an excess of cyclohexanol in boiling toluene gives the same result. Under these reflux conditions, the reaction of GaMe₃ with an excess of PhCH₂OH leads exclusively to another type of sequialkoxides, [Ga{MeGa(OCH₂Ph)₃}₃] ( 6 ). 4 — 6 were characterized by NMR, vibrational and MS spectra, as well as by X‐ray structure determinations. According to this, 4 forms centrosymmetrical and therefore planar Ga₂O₂ four‐membered rings. 5 and 6 possess basically the same structural motif, central M³⁺ ion ( 5 : In³⁺; 6 : Ga³⁺) coordinated by three metalate units ( 5 : [Me₂In(O^cHex)₂]^—; 6 : [MeGa(OCH₂Ph)₃]^—). The central M³⁺ ions have always coordination number (CN) six while the three surrounding metal ions possess CN 4. Because of the spectroscopic findings 6 must exist in two isomers (1:1). The C₃‐symmetrical isomer C₃‐ 6 was characterized by X‐ray analysis, while the isomer C₁‐ 6 could by described mainly by the complex NMR data.     

Synthesen von Verbindungen mit M–N‐Bindungen (M = Li,Ga, In)

Syntheses of Compounds with M–N Bonds (M = Li, Ga, In) The adducts [GaCl₃(HNⁱPr₂)] ( 1 ) and [InCl₃{HN(CH₂Ph)₂}₂] ( 2 ) can be obtained by the reactions of the corresponding metal(III) halides with the amines. The In amide In(N^cHex₂)₃ ( 3 ) can be formed by treatment of InCl₃ with three equivalents of LiN^cHex₂. Reaction with four equivalents of LiN^cHex₂ leads to the same product. However, the treatment of InCl₃ with four equivalents of LiN(CH₂Ph)₂ gives the desired metalate [Li(THF)₄][In{N(CH₂Ph)₂}₄] ( 4 ). From the corresponding reaction of InCl₃ with LiNⁱPr₂ no In‐containing product could be identified. Instead, the aggregate of LiCl with three units of LiNⁱPr₂, [Li₄(NⁱPr₂)₃(THF)₄Cl] ( 5 ), was isolated. 1 – 4 were characterized by NMR, IR and MS techniques as well as by X‐ray structure determinations. According to them, 1 possesses a tetrahedrally coordinated Ga atom, at which two units of 1 are connected by hydrogen bridges to centrosymmetrical dimers. The In atoms in 2 have a trigonal‐bipyramidal coordination sphere; the amine molecules occupy the apical positions. The central metal atom in 3 and the anion of 4 exhibit trigonal‐planar and distorted tetrahedral environments, respectively. The novel structural motif in 5 is the Cl^– ion, only partly surrounded by Li⁺ ions in a strongly distorted trigonal‐bipyramidal fashion. The dominating angle amounts to 165.2(2)°.     

Metallat‐Ionen [Al(OR)4]— als Chelatliganden für Übergangsmetall‐Kationen

Metalat Ions [Al(OR)₄]^— as Chelating Ligands for Transition Metal Cations Waterfree CoCl₂ can be reacted with [{Li(Diglyme)}{Al(O^tBu)₄}] in THF to the complex [Li(THF)₄][{CoCl₂}{Al(O^tBu)₄}]. Addition of diglyme to the reaction mixtures gives the blue compound [Li(diglyme)₂][{CoCl₂}{Al(O^tBu)₄}] ( 1 ). According to this procedure the Fe^II complex [Li(Diglyme)₂][{FeCl₂}₂{Al(O^tBu)₄}] ( 2 ) was formed by treatment of FeCl₂ with Li[Al(O^tBu)₄]. [{Li(diglyme)}{Al(O^tBu)₄}] in THF/diglyme can be used as alkoxide transfer reagent on TiCl₄ to give the neutral complex [TiCl₂(O^tBu)₂(diglyme)] ( 3 ). The sky‐blue salt [Li(THF)₄]₂[{CoCl₂}₃{Al(OCH₂Ph)₄}₂] ( 4 ) was obtained by reaction of Li[Al(OCH₂Ph)₄] with CoCl₂ in THF. By treatment of 4 with diglyme ligand redistribution was observed giving the sky‐blue compound [Li(Diglyme)₂]₂[{CoCl₂}₃{Al(OCH₂Ph)₄}₂] ( 5 ) and the violet salt [Li(Diglyme)₂]₂[Co₂Cl₅(OCH₂Ph)] ( 6 ). A similar salt can be synthesized also directly from Li[Al(O^tBu)₄] and CoCl₂ in diglyme to give [Li(Diglyme)₂]₂[Co₂Cl₅(O^tBu)] ( 7 ). 1 — 7 were characterized by IR spectroscopy, partly by mass spectrometry and X‐ray analyses. UV‐VIS spectra were recorded from 1 and 5 . According to the X‐ray analyses the M^II ions as well as the Al^III ions are coordinated distorted tedrahedrally. In 1 , 2 , 4 und 5 the unit [Al(OR)₄]^— acts a chelating ligand as desired.     

Sulfonyl Fluoride‐Based Prosthetic Compounds as Potential 18F Labelling Agents

Nucleophilic incorporation of [¹⁸F]F^? under aqueous conditions holds several advantages in radiopharmaceutical development, especially with the advent of complex biological pharmacophores. Sulfonyl fluorides can be prepared in water at room temperature, yet they have not been assayed as a potential means to ¹⁸F‐labelled biomarkers for PET chemistry. We developed a general route to prepare bifunctional 4‐formyl‐, 3‐formyl‐, 4‐maleimido‐ and 4‐oxylalkynl‐arylsulfonyl [¹⁸F]fluorides from their sulfonyl chloride analogues in 1:1 mixtures of acetonitrile, THF, or tBuOH and Cs[¹⁸F]F/Cs₂CO_3(aq.) in a reaction time of 15 min at room temperature. With the exception of 4‐N‐maleimide‐benzenesulfonyl fluoride ( 3 ), pyridine could be used to simplify radiotracer purification by selectively degrading the precursor without significantly affecting observed yields. The addition of pyridine at the start of [¹⁸F]fluorination (1:1:0.8 tBuOH/Cs₂CO_3(aq.)/pyridine) did not negatively affect yields of 3‐formyl‐2,4,6‐trimethylbenzenesulfonyl [¹⁸F]fluoride ( 2 ) and dramatically improved the yields of 4‐(prop‐2‐ynyloxy)benzenesulfonyl [¹⁸F]fluoride ( 4 ). The N‐arylsulfonyl‐4‐dimethylaminopyridinium derivative of 4 ( 14 ) can be prepared and incorporates ¹⁸F efficiently in solutions of 100 % aqueous Cs₂CO₃ (10 mg mL^?1). As proof‐of‐principle, [¹⁸F] 2 was synthesised in a preparative fashion [88(±8) % decay corrected (n=6) from start‐of‐synthesis] and used to radioactively label an oxyamino‐modified bombesin(6–14) analogue [35(±6) % decay corrected (n=4) from start‐of‐synthesis]. Total preparation time was 105–109 min from start‐of‐synthesis. Although the ¹⁸F‐peptide exhibited evidence of proteolytic defluorination and modification, our study is the first step in developing an aqueous, room temperature ¹⁸F labelling strategy.     

Organometallische Alkoxo–Indium‐Käfigverbindungen

Compounds with Organometallic Alkoxo–Indium Cages The reaction of InMe₃ with PhCH₂OH (molar ratio 1 : 2) at 20 °C in toluene gives the tetranuclear complex [In{(PhCH₂O)₂InMe₂}₃] ( 2 ) in good yield. A further reaction under reflux conditions was not observed. However, at 160 °C in PhCH₂OH a reaction could be realized, which forms an O‐centred corner‐cutted rhombic dodecahedron, [(MeIn)₅(OCH₂Ph)₈(O)] ( 3 ), under evolution of methane. This In–O skeleton can be degraded with elemental cesium to a hexa‐ and heteronuclear complex [Cs{Cs(THF)}{[MeIn(OCH₂Ph)₂]₄O}] ( 4 ). 2 – 4 were characterized by IR, RE, NMR and MS techniques as well as by X‐ray analyses. According to them 2 can be described as In³⁺ ion, coordinated by three metalate units [Me₂In(OCH₂Ph)₂]^–. 3 loses one MeIn fragment during the transfer of two electrons. Two Cs⁺ ions complete the new rhombic dodecahedron, at which different coordination spheres were observed. One Cs⁺ ion possesses additional contacts to a THF ligand and four π‐electron systems from four phenyl rings, while the THF ligand is missing in the environment of the second alkali cation.     

Two‐dimensional coordination polymeric structures in caesium complexes with ring‐substituted phenoxyacetic acids

The two‐dimensional polymeric structures of the caesium complexes with the phenoxyacetic acid analogues (4‐fluorophenoxy)acetic acid, (3‐chloro‐2‐methylphenoxy)acetic acid and the herbicidally active (2,4‐dichlorophenoxy)acetic acid (2,4‐D), namely poly[[μ₅‐(4‐fluorophenoxy)acetato][μ₄‐(4‐fluorophenoxy)acetato]dicaesium], [Cs₂(C₈H₆FO₃)₂]_n, (I), poly[aqua[μ₅‐(3‐chloro‐2‐methylphenoxy)acetato]caesium], [Cs(C₉H₈ClO₃)(H₂O)]_n, (II), and poly[[μ₇‐(2,4‐dichlorophenoxy)acetato][(2,4‐dichlorphenoxy)acetic acid]caesium], [Cs(C₈H₅Cl₂O₃)(C₈H₆Cl₂O₃)]_n, (III), are described. In (I), the Cs⁺ cations of the two individual irregular coordination polyhedra in the asymmetric unit (one CsO₇ and the other CsO₈) are linked by bridging carboxylate O‐atom donors from the two ligand molecules, both of which are involved in bidentate chelate O_carboxy,O_phenoxy interactions, while only one has a bidentate carboxylate O,O′‐chelate interaction. Polymeric extension is achieved through a number of carboxylate O‐atom bridges, with a minimum Cs...Cs separation of 4.3231 (9) Å, giving layers which lie parallel to (001). In hydrated complex (II), the irregular nine‐coordination about the Cs⁺ cation comprises a single monodentate water molecule, a bidentate O_carboxy,O_phenoxy chelate interaction and six bridging carboxylate O‐atom bonding interactions, giving a Cs...Cs separation of 4.2473 (3) Å. The water molecule forms intralayer hydrogen bonds within the two‐dimensional layers, which lie parallel to (100). In complex (III), the irregular centrosymmetric CsO₆Cl₂ coordination environment comprises two O‐atom donors and two ring‐substituted Cl‐atom donors from two hydrogen bis[(2,4‐dichlorophenoxy)acetate] ligand species in a bidentate chelate mode, and four O‐atom donors from bridging carboxyl groups. The duplex ligand species lie across crystallographic inversion centres, linked through a short O—H...O hydrogen bond involving the single acid H atom. Structure extension gives layers which lie parallel to (001). The present set of structures of Cs salts of phenoxyacetic acids show previously demonstrated trends among the alkali metal salts of simple benzoic acids with no stereochemically favourable interactive substituent groups for formation of two‐dimensional coordination polymers.     

Amidoverbindungen von Aluminium und Gallium

Amido Derivatives of Aluminium and Gallium The treatment of GaCl₃ with LiN^cHex₂ (^cHex = C₆H₁₁) in the molar ratio 1 : 3 or 1 : 4 in THF at 20 °C gives the gallium amide Ga(N^cHex₂)₃ ( 1 ) which is monomer in solution and the solid state. Under similar conditions the reaction of AlCl₃ and GaCl₃ with LiN(CH₂Ph)₂ in the molar ration of 1 : 4 leads to the amido metalates [Li(THF)₄][M{N(CH₂Ph)₂}₄] (M = Al ( 2 ), Ga ( 3 )). 1 – 3 have been characterized by NMR, IR and MS techniques as well as by X‐Ray analyses. According to them 2 and 3 consist of separate ions [Li(THF)₄]⁺ and [M{N(CH₂Ph)₃}₄]^–. The reason for the monomeric character of 1 is the sterical demand of the N^cHex₂ group.     

A one‐dimensional zinc(II) coordination polymer with a three‐dimensional supramolecular architecture incorporating 1‐[(1H‐benzimidazol‐2‐yl)methyl]‐1H‐tetrazole and adipate

The synthesis of coordination polymers or metal–organic frameworks (MOFs) has attracted considerable interest owing to the interesting structures and potential applications of these compounds. It is still a challenge to predict the exact structures and compositions of the final products. A new one‐dimensional coordination polymer, catena‐poly[[[bis{1‐[(1H‐benzimidazol‐2‐yl)methyl]‐1H‐tetrazole‐κN³}zinc(II)]‐μ‐hexane‐1,6‐dicarboxylato‐κ⁴O¹,O^1′:O⁶,O^6′] monohydrate], {[Zn(C₆H₈O₄)(C₉H₈N₆)₂]·H₂O}_n, has been synthesized by the reaction of Zn(Ac)₂ (Ac is acetate) with 1‐[(1H‐benzimidazol‐2‐yl)methyl]‐1H‐tetrazole (bimt) and adipic acid (H₂adi) at room temperature. In the polymer, each Zn^II ion exhibits an irregular octahedral ZnN₂O₄ coordination geometry and is coordinated by two N atoms from two symmetry‐related bimt ligands and four O atoms from two symmetry‐related dianionic adipate ligands. Zn^II ions are connected by adipate ligands into a one‐dimensional chain which runs parallel to the c axis. The bimt ligands coordinate to the Zn^II ions in a monodentate mode on both sides of the main chain. In the crystal, the one‐dimensional chains are further connected through N—H…O hydrogen bonds, leading to a three‐dimensional supramolecular architecture. In addition, the title polymer exhibits fluorescence, with emissions at 334 and 350 nm in the solid state at room temperature.     

Neue molekulare Indium‐Zinn‐Sauerstoff‐ und Indium‐Zinn‐Natrium‐Sauerstoff‐Chlor‐Cluster

Abstract. The five‐membered heteroelement cluster THF · Cl₂In(O^tBu)₃Sn reacts with the sodium stannate [Na(O^tBu)₃Sn]₂ to produce either the new oxo‐centered alkoxo cluster ClInO[Sn(O^tBu)₂]₃ ( 1 ) (in low yield) or the heteroleptic alkoxo cluster Sn(O^tBu)₃InCl₃Na[Sn(O^tBu)₂]₂ ( 2 ). X‐ray diffraction analyses reveal that in compound 1 the polycyclic entity is made of three tin atoms which together with a central oxygen atom form a trigonal, almost planar triangle, perpendicular to which a further indium atom is connected through the oxygen atom. The metal atoms thus are arranged in a Sn₃In pyramid, the edges of which are all saturated by bridging tert‐butoxy groups. The indium atom has a further chloride ligand. Compound 2 has two trigonal bipyramids as building blocks which are fused together at a six coordinate indium atom. One of the bipyramids is of the type SnO₃In with tert‐butyl groups on the oxygen atoms, while the other has the composition InCl₃Na with chlorine atoms connecting the two metals. The sodium atom in 2 has further contacts to two plus one alkoxide groups which are part of a[Sn(O^tBu)₂]₂ dimer disposing of a Sn₂O₂ central cycle. The hetero element cluster in 2 thus combines three closed entities and its skeleton SnO₃InCl₃NaO₂Sn₂O₂ consists of three different metallic and two different non‐metallic elements.     

Synthese eines hexanuklearen Calcium–Phosphor‐Käfigs über heteroleptische Calcium‐amid‐phosphanid‐Vorstufen

Synthesis of a Hexanuclear Calcium–Phosphorus‐Cage The metalation of tri(tert‐butyl)silylphosphane with calcium bis[bis(trimethylsilyl)amide] yields the dimer {(Me₃Si)₂N–Ca(THF)[μ‐P(H)Si^tBu₃]}₂ ( 1 ). In THF monomerization occurs and dismutation reactions lead to the homoleptic compounds, namely (THF)₂Ca[N(SiMe₃)₂]₂ and (THF)₄Ca[P(H)Si^tBu₃]₂. In toluene, 1 undergoes dismutation reactions, bis(tetrahydrofuran)calcium bis[bis(trimethylsilyl)amide] is regained and [(Me₃Si)₂N–Ca(THF)]₂Ca[P(H)Si^tBu₃]₄ ( 2 ) precipitates. At raised temperatures, 2 undergoes a homometallic metalation with the loss of two equivalents of HN(SiMe₃)₂ and dimerizes. The thus formed cage compound (THF)₂Ca₆[PSi^tBu₃]₄[P(H)Si^tBu₃]₄ ( 3 ) with a central Ca₄P₄ heterocubane moiety crystallizes upon cooling of the toluene solution. The molecular structures of 2 and 3 were determined.     

A one‐dimensional lead(II) coordination polymer with terminal and bridging 5‐carboxy‐2‐(pyridin‐3‐yl)‐1H‐imidazole‐4‐carboxylate ligands

In the coordination polymer catena‐poly[[[diaqua[5‐carboxy‐2‐(pyridin‐3‐yl)‐1H‐imidazole‐4‐carboxylato‐κ²N³,O⁴]lead(II)]‐μ‐5‐carboxy‐2‐(pyridin‐3‐yl)‐1H‐imidazole‐4‐carboxylato‐κ³N³,O⁴:N²] dihydrate], {[Pb(C₁₀H₆N₃O₄)(H₂O)₂]·2H₂O}_n, the two 5‐carboxy‐2‐(pyridin‐3‐yl)‐1H‐imidazole‐4‐carboxylate ligands have different coordination modes, one being terminal and the other bridging. The bridging ligand links Pb^II cations into one‐dimensional coordination polymer chains. The structure is also stabilized by intra‐ and interchain π–π stacking interactions between the pyridine rings, resulting in the formation of a two‐dimensional network. Extensive hydrogen‐bonding interactions lead to the formation of a three‐dimensional supramolecular network.     

Synthesis,Crystal Structures,and Thermolysis Studies of Heteronuclear Transition Metal Aluminum Alcoholates

Heteronuclear alcoholate complexes [M{Al(OiPr)₄}₂(bipy)] ( 2-M , M = Fe, Co, Ni, Cu, Zn) and [M{Al(OcHex)₄}₂(bipy)] ( 3-M , M = Fe, Co, Ni, Zn) are formed by adduct formation of [M{Al(OiPr)₄}₂] ( 1-M , M = Fe, Co, Ni, Cu, Zn) with 2,2'-bipyridine and transesterification reaction with cHexOAc. According to crystal structure analyses, in 2-M and 3-M the central transition metal ion M²⁺ is coordinated by two chelating Al(OR)₄^– moieties and one bipyridine ligand in an octahedral arrangement. Treating 1-Cu with 2,2'-bipyridine leads to a reduction process, whereat the intermediate [Cu{Al(OiPr)₄}(bipy)₂][Al(OiPr)₄] ( 4 ) could be structurally characterized. During conversion of the iso-propanolate ligands in 1-Cu to cyclohexanolate ligands, Cu²⁺ is reduced to Cu⁺ forming [Cu{Al(O^cHex)₄}(py)₂] ( 5 ). UV/Vis-spectra and results of thermolysis studies by TG/DTA-MS are reported.     

Polysulfonylamine. CLXV [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 14 [1] Cs3Ag[(MeSO2)2N]4 und CsAg[(MeSO2)2N]2: Ein dreidimensionales und ein schichtförmiges Koordinationspolymer mit Bis(dimesylamido‐N)argentat‐Baugruppen

Polysulfonylamines. CLXV. Crystal Structures of Metal Di(methanesulfonyl)amides. 14. Cs₃Ag[(MeSO₂)₂N]₄ and CsAg[(MeSO₂)₂N]₂: A Three‐Dimensional and a Layered Coordination Polymer Containing Bis(dimesylamido‐N)argentate Building Blocks Serendipitous formation pathways and low‐temperature X‐ray structures are reported for the coordination compounds Cs₃A₂[AgA₂] ( 1 ) and Cs[AgA₂] ( 2 ), where A^— represents the pentadentate dimesylamide ligand (MeSO₂)₂N^—. Both phases (monoclinic, space group C2/c, Z′ = 1/2) contain inversion‐symmetric bis(dimesylamido‐N)argentate units displaying exactly linear N—Ag—N cores and short, predominantly covalent Ag—N bonds [ 1 : 213.5(2), 2 : 213.35(12) pm]; in each case, the coordination number of the silver ion is extended to 2 + 6 by four internal and two external Ag···O secondary interactions. The three‐dimensional coordination polymer 1 is built up from alternating layer substructures [{Cs(1)}{A}_4/2]^— with Cs(1) lying on twofold rotation axes and [{Cs(2)}₂{AgA₂}_4/4]⁺ with Cs(2) occupying general positions. Within the substructural layers, both types of cesium cation have approximately planar O₄ environments, whereas the final coordination spheres including interlayer bonds are extended to O₆ for Cs(1) and to O₈N for Cs(2). Compound 2 , in contrast, forms a genuine layer structure. The layers are constructed from Cs⁺ chains located on twofold rotation axes, alternating with [AgA₂]^— stacks reinforced by Ag···O secondary interactions and weak C—H···O hydrogen bonds; Cs⁺ is embedded in an O₈ environment. Both structures are pervaded by a three‐dimensional C—H···O network.     

Synthese und Kristallstruktur von [(PhCH2)2GaF(tBuNH2)]2 · 2 THF

Synthesis and Crystal Structure of [(PhCH₂)₂GaF(^tBuNH₂)]₂ · 2 THF (PhCH₂)₂GaF reacts with ^tBuNH₂ to the adduct [(PhCH₂)₂GaF(^tBuNH₂)] ( 1 ). 1 was characterized by NMR, IR and MS techniques. 1 can be recrystallized from THF forming crystals of [ 1 ]₂ · 2 THF. According to an X-ray structure analysis [ 1 ]₂ · 2 THF consists of dimers of 1 formed by hydrogen bridges. The THF molecules are coordinated to [ 1 ]₂ by hydrogen bridges, too.     

A one‐dimensional nickel(II) coordination polymer containing 2,6‐dipicolinate and dipyrido[3,2‐a:2′,3′‐c]phenazine

A new coordination polymer, catena‐poly[[(dipyrido[3,2‐a:2′,3′‐c]phenazine‐κ²N,N′)nickel(II)]‐μ‐2,6‐dipicolinato‐κ⁴O²,N,O⁶:O^2′], [Ni(C₇H₃NO₄)(C₁₈H₁₀N₄)]_n, exhibits a one‐dimensional structure in which 2,6‐dipicolinate acts as a bridging ligand interconnecting adjacent nickel(II) centers to form a chain structure. The asymmetric unit contains one Ni^II center, one dipyrido[3,2‐a:2′,3′‐c]phenazine ligand and one 2,6‐dipicolinate ligand. Each Ni^II center is six‐coordinated and surrounded by three N atoms and three O atoms from one dipyrido[3,2‐a:2′,3′‐c]phenazine ligand and two different 2,6‐dipicolinate ligands, leading to a distorted octahedral geometry. Adjacent chains are linked by π–π stacking interactions and weak interactions to form a three‐dimensional supramolecular network.     

Nucleophilic Reactivity of a Nitride‐Bridged Diuranium(IV) Complex: CO2 and CS2 Functionalization

Thermolysis of the nitride‐bridged diuranium(IV) complex Cs{(μ‐N)[U(OSi(O^tBu)₃)₃]₂} ( 1 ) showed that the bridging nitride behaves as a strong nucleophile, promoting N?C bond formation by siloxide ligand fragmentation to yield an imido‐bridged siloxide/silanediolate diuranium(IV) complex, Cs{(μ‐N^tBu)(μ‐O₂Si(O^tBu)₂)U₂(OSi(O^tBu)₃)₅}. Complex 1 displayed reactivity towards CS₂ and CO₂ at room temperature that is unprecedented in f‐element chemistry, affording diverse N‐functionalized products depending on the reaction stoichiometry. The reaction of 1 with two equivalents of CS₂ yielded the thiocyanate/thiocarbonate complex Cs{(μ‐NCS)(μ‐CS₃)[U(OSi(O^tBu)₃)₃]₂} via a putative NCS^?/S^2? intermediate. The reaction of 1 with one equivalent of CO₂ resulted in deoxygenation and N?C bond formation, yielding the cyanate/oxo complex Cs{(μ‐NCO)(μ‐O)[U(OSi(O^tBu)₃)₃]₂}. Addition of excess CO₂ to 1 led to the unprecedented dicarbamate product Cs{(μ‐NC₂O₄)[U(OSi(O^tBu)₃)₃]₂}.     

Synthese und Struktur von Sr6P8‐Polyedern in gemischten Phosphaniden/Phosphandiiden des Strontiums

Synthesis and Structures of Sr₆P₈ Polyhedra in Mixed Phosphanides/Phosphandiides of Strontium The strontiation of H₂PSiⁱPr₃ ( 1 ) with (THF)₂Sr[N(SiMe₃)₂]₂ in THF yields colorless tetrakis(tetrahydrofuran‐O)strontium bis(triisopropylsilylphosphanide) ( 3 ). The central alkaline earth metal atom has an octahedral environment with the phosphanide ligands in trans position. The homometalation in toluene leads to the elimination of 1 and THF. Cooling of this solution gives crystals of colorless tetrakis(tetrahydrofuran‐O)hexastrontium‐tetrakis(triisopropylsilylphosphanide)‐tetrakis(triisopropylsilylphosphandiide) ( 4 ). The equimolar reaction of H₂PSi^tBu₃ ( 2 ) with (THF)₂Sr[N(SiMe₃)₂]₂ in toluene yields in the first step heteroleptic dimeric {(Me₃Si)₂NSr(THF)₂[P(H)Si^tBu₃]}₂ ( 5 )₂. This compounds monomerizes in THF to (Me₃Si)₂N–Sr(THF)₄[P(H)Si^tBu₃] ( 6 ), which forms an equilibrium with the homoleptic dismutation products (THF)₂Sr[N(SiMe₃)₂]₂ and (THF)₄Sr[P(H)Si^tBu₃]₂ ( 7 ). Compound ( 5 )₂ undergoes a intramolecular strontiation and bis(tetrahydrofuran‐O)hexastrontium‐tetrakis[tri(tert‐butyl)silylphosphanide]‐tetrakis[tri(tert‐butyl)silylphosphandiide] ( 8 ) is isolated. The central Sr₆P₈‐polyhedra of 4 and 8 are very similar.     

Chirale Gallium‐ und Indium‐Alkoxometallate

Chiral Gallium and Indium Alkoxometalates Li₂(S)‐BINOLate ((S)‐BINOL = (S)‐(–)‐2,2′‐Dihydroxy‐1,1′‐binaphthyl) generated by dilithiation of (S)BINOL with two equivalents ⁿBuLi was reacted with GaCl₃ und InCl₃ in THF to the alkoxometalates [{Li(THF)₂}{Li(THF)}₂{Ga((S)‐BINOLate)₃}] ( 1 ) and [{Li(THF)₂}₂{Li(THF)}{In((S)‐BINOLate)₃}] · [{Li(THF)₂}{Li(THF)}₂{In((S)‐ BINOLate)₃}]₂ ( 3 ), respectively. 1 and 3 crystallize from THF/toluene mixtures as 1 · 2 toluene and 3 · 8 toluene. The treatment of PhCH₂GaCl₂ with Li₂(S)‐BINOLate in THF under reflux, followed by recrystallization of the product from DME gives the gallate [{Li(DME)}₃{Ga((S)BINOLate)₃}] · 1.5 THF ( 2 · 1.5 THF). 1 – 3 were characterized by NMR, IR and MS techniques. In addition, 1 · 2 toluene, 2 · 1.5 THF and 3 · 8 toluene were investigated by X‐ray structure analyses. According to them, a distorted octahedral coordination sphere around the group 13 metal was formed, built‐up by three BINOLate ligands. The three Li⁺ counter ions act as bridging units by metal‐oxygen coordination. The coordination sphere of the Li⁺ ions was completed, depending on the available space, by one or two THF ligands ( 1 · 2 toluene, 3 · 8 toluene) and one DME ligand ( 2 · 1.5 THF), respectively. The sterical dominance of the BINOLate ligands can be shown by the almost square‐planar coordination of the Li⁺ ions in 2 · 1.5 THF giving a small twisting angle of only 17°.