Synthese und Charakterisierung neuer cyclischer und käfigartiger Indium‐Phosphor‐ und Indium‐Arsen‐Verbindungen

Synthesis and Characterization of New Cyclic and Cage‐like Indium — Phosphorus and Indium — Arsenic Compounds The reaction of InEt₃ with H₂ESiiPr₃ initially yields the cyclic compound [Et₂InP(H)SiiPr₃]₂ ( 2 ). 2 appears as a mixture of cis and trans isomers and has been characterized by ³¹P‐NMR spectroscopy, IR spectroscopy, and mass spectrometry. 2 decomposes in solution under elimination of ethane during a few days to form [EtInPSiiPr₃]₄ ( 3 ) with a cage‐like structure. The analogous arsenic compound [EtInAsSiiPr₃]₄ ( 4 ) can be prepared by reaction of InEt₃ with H₂AsSiiPr₃. Central structural motif of 3 and 4 is an In₄E₄ heterocubane like structure (E = P, As), whereas the reaction of InEt₃ with H₂PSiMe₂Thex (Thex = CMe₂iPr) yields [EtInPSiMe₂Thex]₆ ( 5 ) with a hexagonal prismatic structure.     

Synthese,Kristallstrukturen und quantenchemische Untersuchung von Verbindungen mit leiterartigem Al4P4‐ und hexagonal prismatischem Al6P6‐Grundgerüst

The reaction of AlCl₃ with Li₂PR (R = SiiPr₃, SiMeiPr₂) in a mixture of heptane and ether yields in the polycyclic compounds [(AlCl)₄(μ₃‐PR)₂(μ‐PR)₂(Et₂O)₂]( 1a : R = SiiPr₃; 1b : SiMeiPr₂) with a ladder‐shaped Al₄P₄ core. The coordination sphere of the outer aluminium atoms in these compounds is completed by ether ligands. In contrast, the reaction of AlCl₃ with Li₂PSiiPr₃ in pure heptane yields in the formation of the hexagonal prismatic compound [(AlCl)₆(μ₃‐PSiiPr₃)₆]( 2 ). 1 and 2 were characterized by single crystal X‐ray diffraction analysis as well as by ³¹P{1H} and ²⁷Al NMR spectroscopy. The structure determining effect of the solvent can be rationalized by quantumchemical calculations, which also show that the hexagonal prismatic structure is the most stable of the investigated oligomers in absence of ether.     

Reaktionen von NaAlH4 mit primären Silylphosphanen und ‐arsanen: Synthese und Kristallstruktur eines cyclischen Natriumphosphanylalanats und eines polycyclischen Natriumarsanylalanats

Reaction of NaAlH4 with Primer Silylphosphines and Silylarsines: Synthesis and Crystal Structure of a Cyclic Sodium Phosphanylalanate and a Polycyclic Sodium Arsanylalanate The reaction of sodium aluminium hydride with H₂PSiMe₃ in the molar ratio 1:4 yields the compound [H₂Al{P(SiMe₃)₂}₂Na(dme)₂] ( 1 ). Central structural motif of this compound in a four‐membered AlP₂Na ring. Surprisingly the phosphorus atoms in the ring wear two exocyclic silylgroups each. From the reaction of NaAlH₄ with the primer silylarsine H₂AsSiiPr₃ in THF the ionic compound 2 can be obtained. In this compound cyclic [(H₂Al)₃(AsSiiPr₃)₃]^3‐ anions coordinate the sodium counter‐ions by the hydride ligands as well as by the arsenic atoms.     

Dimethylerdmetall‐Heterocyclen als Derivate trimethylsilylierter, ‐germylierter und ‐stannylierter Phosphane und Arsane – Synthesen,Spektren und Strukturen

Dimethyl Earth‐Metal Heterocycles – Derivatives of Trimethyl‐silylated, ‐germylated, and ‐stannylated Phosphanes and Arsanes – Syntheses, Spectra, and Structures The organo earth‐metal heterocycles [Me₂M^III–E(M^IVMe₃)₂]_n with M^III = Al, Ga, In; E = P, As; M^IV = Si, Ge, Sn and n = 2, 3 (Me = CH₃) have been prepared from the dimethyl metal compounds Me₂M^IIIX (X = Me, H, Cl, OMe, OPh) and the pnicogen derivatives H_nE(M^IVMe₃)_3–n (n = 0, 1) according to known preparation methods. The mass, ¹H, ¹³C, ³¹P, ²⁹Si, ¹¹⁹Sn nmr, as well as the ir and Raman spectra have been discussed comparatively; selected representatives are characterized by X‐ray structure analyses. The dimeric species with four‐membered (E–M^III)₂ rings are isotypic and crystallize in the triclinic space group P1, the trimer [Me₂In–P(SnMe₃)₂]₃ with a strongly puckered (In–P)₃‐ring skeleton crystallizes with two formula units per cell in the same centrosymmetric triclinic space group.     

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.     

Offenkettige und cyclische As‐funktionalisierte Stannylarsine: Darstellung,Reaktionen und Struktur

Open‐Chain and Cyclic As‐functionalized Stannylarsines: Synthesis, Reactions, and Structure ^tBu₃SnAsH₂ ( 1 ) reacts with MeLi to form the lithium compound ^tBu₃SnAsHLi which reacts with ^tBu₂SnCl₂ to give the AsH‐functionalized bis(arsino)stannane ^tBu₂Sn(AsHSn^tBu₃)₂ ( 2 ). Metallation of diarsadistannetane (^tBu₂SnAsH)₂ ( 3 ) with two equivalents of ^tBuLi yields the dilithio compound (^tBu₂SnAsLi)₂ which reacts with Me₃SiCl or Me₃SnCl to give the corresponding As,As′‐bis‐substituted diarsadistannetanes (^tBu₂SnAsSiMe₃)₂ ( 4 ) and (^tBu₂SnAsSnMe₃)₂ ( 5 ), respectively. The novel compounds are characterized by NMR (¹H, ¹¹⁹Sn) and mass spectroscopy, ring compounds 4 and 5 further by X‐ray structure analysis. In the solid state both ring compounds contain molecules with planar tin‐arsenic rings and two trans‐configurated Me₃Si‐ or Me₃Sn‐ring substituents (space group P2₁/n (No. 14), Z = 2).     

Intramolekular schwefelstabilisierte Aluminium‐ und Galliumalkyle

Intramolecularly Sulfur stabilized Aluminum and Gallium Alkyl Derivatives The intramolecularly sulfur stabilized organoaluminum and organogallium compounds Me₂Al(CH₂)₃SEt ( 1 ), Me₂Ga(CH₂)₃SEt ( 2 ), MeClAl(CH₂)₃SEt ( 3 ), MeClGa(CH₂)₃SEt ( 4 ), Cl₂Al(CH₂)₃SEt ( 5 ), and Cl₂Ga(CH₂)₃SEt ( 6 ) are synthesized from Me₂MCl, MeMCl₂, and MCl₃ (M = Al, Ga), respectively, and ClMg(CH₂)₃SEt. The reaction of 5 and of 6 with BrMg(CH₂)₅MgBr yields (CH₂)₅Al(CH₂)₃SEt ( 7 ) and (CH₂)₅Ga(CH₂)₃SEt ( 8 ), respectively. AlCl₃ and GaCl₃ react with two as well as three equivalents of ClMg(CH₂)₃SEt forming ClAl[(CH₂)₃SEt]₂ ( 9 ) and ClGa[(CH₂)₃SEt]₂ ( 10 ) as well as Al[(CH₂)₃SEt]₃ ( 11 ) and Ga[(CH₂)₃SEt]₃ ( 12 ), respectively. The compounds were characterized by elemental analyses, mass spectroscopy, ¹H, ¹³C, and ²⁷Al NMR investigations as well as 6 by single crystal X‐ray structure analysis.     

Der erste viergliedrige Al/P‐Ring,der von drei Phosphoratomen und einem Aluminiumatom gebildet wird: Synthese und Kristallstruktur von [Cp*Al(PtBu)3]

The First Four‐Membered Al/P Ring formed by three Phosphorus Atoms nd one Aluminium Atom: Synthesis and Crystal Structure of [Cp*Al(P t Bu)₃] (AlCp*)₄ reacts with (PtBu)₃ at 90 °C to form the new cyclic Al/P‐compound 1,2,3‐tris‐t‐butyl‐tri‐phospha‐4‐pentamethylcyclopentadienylaluminetane: [Cp*Al(PtBu)₃] ( 1 ). 1 has been characterised by single crystal x‐ray diffraction, ³¹P{¹H}‐NMR spectroscopy as well as mass spectroscopy. It consists of a folded four‐membered AlP₃‐ring and differs therefore from all Al/P‐compounds known so far, which always show alternating Al‐P‐positions. 1 crystallises in the orthorhombic spacegroup P2₁2₁2₁, the lattice constants are: a = 9.067 pm, b = 16.212 pm, c = 17.449 pm, α = β = γ = 90°.     

Synthese und Struktur von η1‐Phosphaallyl‐, η1‐Arsaallylund η1‐Stibaallyleisen‐Komplexen [(η5‐C5Me5)(CO)2Fe–E(SiMe3)C(OSiMe3)=CPh2] (E = P,As, Sb)

Syntheses and Structures of η¹‐Phosphaallyl, η¹‐Arsaallyl, and η¹‐Stibaallyl Iron Complexes [(η⁵‐C₅Me₅)(CO)₂Fe–E(SiMe₃)C(OSiMe₃)=CPh₂] (E = P, As, Sb) The reaction of equimolar amounts of [(η⁵‐C₅Me₅)(CO)₂Fe–E(SiMe₃)₂] ( 1 a : E = P; 1 b : As; 1 c : Sb) and diphenylketene afforded the η¹‐phosphaallyl‐, η¹‐arsaallyl‐, and η¹‐stibaallyl complexes [(η⁵‐C₅Me₅)(CO)₂Fe–E(SiMe₃)C(OSiMe₃)=CPh₂] ( 2 a : E = P; 2 b : As; 2 c : Sb). The molecular structures of 2 b and 2 c were elucidated by single crystal X‐ray analyses.     

Darstellung,Eigenschaften und Molekülstrukturen von Dimethylaminomethylferrocenyl‐Verbindungen ausgewählter Elemente der Gruppen 13 und 14

Preparation, Properties, and Molecular Structures of Dimethylaminomethyl Ferrocenyl Compounds of selected Elements of Group 13 and 14 Dimethylmetalchlorides of gallium and indium react with dimethylaminomethylferrocenyllithium (FcNLi) to give the corresponding dimethylmetaldimethylaminomethylferrocenes 1 and 2 [Me₂MFcN; M=Ga, In]. In a similar manner dialkylmetaldichlorides of germanium and tin yield the expected chlordialkylmetaldimethylaminomethylferrocenes 3 – 5 [R₂(Cl)MFcN; M=Ge; R = Me ( 3 ), M=Sn; R=Me ( 4 ), Ph ( 5 )]. In a reaction of Me₃Al and Me₂AlCl with dimethylaminomethylferrocene the formation of the 1 : 1 adducts 7 and 8 could be observed. All compounds were characterised by ¹H and ¹³C nmr spectroscopy. The molecular structures of 1 , 3 , 4 and 7 were determined. 3 and 4 build in contrast to 1 monomeric molecules with chelat rings as a result of the M–N coordination. Compound 7 consist of monomeric molecules with 4 coordinated Al atoms.     

Aluminium‐Mediated Carbon Dioxide Reduction by an Isolated Monoalumoxane Anion

The deoxygenative conversion of carbon dioxide to carbon monoxide is promoted by the aluminyl anion [Al(NON^Ar)]^? (NON^Ar=[O(SiMe₂NAr)₂]^2?, Ar=2,6‐iPr₂C₆H₃). The reaction proceeds via the isolable monoalumoxane anion [Al(NON^Ar)(O)]^?, containing a terminal aluminum‐oxygen bond. This species reacts with a second equivalent of carbon dioxide to afford the carbonate [Al(NON^Ar)(CO₃)]^?, and with nitrous oxide to generate the hyponitrite anion, [Al(NON^Ar)(κ²O,O′‐N₂O₂)]^?.     

Bisaminophosphane – Synthese,Struktur und Reaktivität

Bisaminophosphanes – Synthesis, Structure, and Reactivity Different pathways for the synthesis of bis(alkylamino)phosphanes RP(N(H)R′)₂ are described. t‐BuP(N(H)‐ Dipp)₂ (Dipp = 2,6‐i‐Pr₂–C₆H₃) was structurally characterized by single crystal X‐ray diffraction. The reactivity of the compounds was examplarily investigated using t‐BuP(N(H)t‐Bu)₂. Its reaction with Me₃Al and R₂AlH (R = Me, Et, i‐Bu) in 1 : 1 and 1 : 2 stoichiometrie yield monosubstituted compounds of the type t‐BuP(N(H)t‐Bu)(N(AlR₂)t‐Bu).