Reaktionen von R4Sb2 (R = Me,Et) mit (Me3SiCH2)3M (M = Ga,In) und Kristallstrukturen von [(Me3SiCH2)2InSbMe2]3 und [(Me3SiCH2)2GaOSbEt2]2

Reactions of R₄Sb₂ (R = Me, Et) with (Me₃SiCH₂)₃M (M = Ga, In) and Crystal Structures of [(Me₃SiCH₂)₂InSbMe₂]₃ and [(Me₃SiCH₂)₂GaOSbEt₂]₂ The reaction of (Me₃SiCH₂)₃In with Me₂SbSbMe₂ gives [(Me₃SiCH₂)₂InSbMe₂]₃ ( 1 ) and Me₃SiCH₂SbMe₂. [(Me₃SiCH₂)₂GaOSbEt₂]₂ ( 2 ) is formed by the reaction of (Me₃SiCH₂)₃Ga with Et₂SbSbEt₂ and oxygen. The syntheses and the crystal structures of 1 and 2 are reported.     

Monomere Dialkylmetallkomplexe des Typs R2M(NR′)2XR mit M = Al,Ga, In,TI; X = S,C und R,R′ = Alkyl und Silyl

Monomeric Dialkyl Metal Complexes of the R₂M(NR′)₂XR Type with M = Al, Ga, In, Tl; X = S, C and R, R′ = Alkyl and Silyl N,N′-Bis(trimethylsilyl)sulfurdiimide reacts with the trimethyl derivatives of aluminium, gallium, and indium within insertion. Hereby monomeric sulfinic acid imidamidates Me₂M(NSiMe₃)₂SMe (Me = CH₃) are formed. The lithium amidinates Li(NR′)₂CMe (R′ = i-C₃H₇ and SiMe₃) are formed likewise by insertion reactions with LiMe and the corresponding carbodiimides R′N?C?NR′ and were used in reactions with R₂MCl (M = Al to Tl) to synthesize dialkyl metal amidinates R₂M(NR′)₂CMe. The NMR (¹H and ¹³C) and the vibrational spectra (IR and Raman) are discussed and applied to describe the structure of these chelat complexes.     

Synthesis and Crystal Structures of Aluminum,Gallium and Indium Complexes with Chelating Me2Si(NPh)22– Ligands

The reaction of ECl₃ (E = Al, Ga) with two equivalentsof Li₂Me₂Si(NPh)₂ (in diethyl ether/n‐hexane) leads to the formation of bis‐chelate complexes [Li(OEt₂)₃][E{Me₂Si(NPh)₂}₂] (E = Al ( 1 ), Ga ( 2 )). Compounds 1 and 2 crystallize isotypically in the monoclinic system with a = 1136.42(6), b = 3267.9(1), c = 1360.37(8) pm, β = 94.320(7)° for 1 and a = 1140.88(6), b = 3261.7(2), c = 1360.20(8) pm, β = 94.641(7)° for 2 . Both the compounds display a distorted tetrahedral coordination of the central metal atom to give a spirocyclic EN₄Si₂ core. The Al–N bond lengths are in the range of186.5–186.9 pm and for the Ga–N distances values between 192.3and 193.1 pm are observed. Treatment of InCl₃ with three equivalents of Li₂Me₂Si(NPh)₂ yields the tris‐chelate [{Li(OEt₂)}₃In{Me₂Si(NPh₂)}₃] 3 . Compound 3 crystallizes in the trigonal crystal system , space group R$\bar{3}$ c with a = 1852.4(1), and c = 3300.2(2) pm. The central indium atom is coordinated by threeMe₂Si(NPh)₂^2– ligands in a distorted octahedral arrangement withIn–N bond lengths of 230.8 pm.     

[Ga6R8]2– (R = SiPh2Me): Eine metalloide Clusterverbindung mit einem unerwarteten Ga6‐Gerüst

[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 (C_2h) could also be realized with the help of DFT calculation. DFT calculations furthermore show that 1 is energetically favoured against an octahedral Ga₆R₆^2– 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.     

Gallium‐Indium Ordering in the Complex [Ni2Ga3In] Network of GdNi2Ga3In

Polycrystalline samples of the isotypic quaternary compounds RENi₂Ga₃In (RE = Y, Gd – Tm) were obtained by arc‐melting of the elements. Crystals of the gadolinium compound were found by slow cooling of an arc‐melted button of the initial composition “GdNiGa₃In”. All samples were characterized by powder X‐ray diffraction. The structure of GdNi₂Ga_2.89In_1.11 was refined from single‐crystal X‐ray diffractometer data: new type, Pnma, a = 2426.38(7), b = 418.17(2), c = 927.27(3) pm, wR₂ = 0.0430, 1610 F² values and 88 variables. Two of the six crystallographically independent gallium sites show a small degree of Ga/In mixing. The nickel atoms show tricapped trigonal prismatic coordination by gadolinium, gallium, and indium. Together, the nickel, gallium, and indium atoms build up a complex three‐dimensional [Ni₂Ga₃In]^δ– network, which leaves cages for the gadolinium atoms. The indium atoms form zigzag chains with In–In distances of 337 pm. The crystal chemical similarities of the polyhedral packing in the GdNi₂Ga₃In and La₄Pd₁₀In₂₁ structures are discussed.     

Neue viergliedrige GaE‐ und InE‐Ringverbindungen: Synthese und Kristallstruktur von [Et2InE(SiMe3)2]2 und [GaCl(PtBu2Me)E(SiMe3)]2 (E = P,As)

New GaE and InE Four Membered Ring Compounds: Syntheses and Crystal Structures of [Et₂InE(SiMe₃)₂]₂ and [GaCl(P t Bu₂Me)E(SiMe₃)]₂ (E = P, As) Et₃In · PR₃ (R = Et, iPr) reacts with H₂ESiMe₃ under liberation of C₂H₆ and EH₃ to form the cyclic compounds [Et₂InE(SiMe₃)₂]₂ ( 1 a : E = P, 1 b : E = As). 1 consists of a planar four membered In₂E₂ ring in which the indium and phosphorus or arsenic atoms are four coordinated. In contrast, the phosphorus/arsenic atoms in [GaCl(PtBu₂Me)E(SiMe₃)]₂ ( 2 a : E = P, 2 b : E = As) only have the coordination number three. 2 results from the reaction of GaCl₃ · PtBu₂Me with As(SiMe₃)₃ or Li₂PSiMe₃ respectively, and displays a folded four membered Ga₂E₂ ring as central structural motif. 1 and 2 have been characterised by single crystal X‐ray diffraction analysis as well as ¹H and ³¹P{¹H} NMR spectroscopy.     

Studien zur Reaktion von [Me2AlP(SiMe3)2]2 mit basenstabilisierten Organogalliumchloriden und ‐hydriden

Investigations on the Reactivity of [Me₂AlP(SiMe₃)₂]₂ with Base‐stabilized Organogalliumhalides and ‐hydrides [Me₂AlP(SiMe₃)₂]₂ ( 1 ) reacts with dmap?Ga(Cl)Me₂, dmap?Ga(Me)Cl₂, dmap?GaCl₃ and dmap?Ga(H)Me₂ with Al‐P bond cleavage and subsequent formation of heterocyclic [Me₂GaP(SiMe₃)₂]₂ ( 2 ) as well as dmap?AlMe_xCl_3?x (x = 3 8 ; 2 3 ; 1 4 ; 0 5 ). The reaction between equimolar amounts of dmap?Al(Me₂)P(SiMe₃)₂ and dmap?Ga(t‐Bu₂)Cl yield dmap?Ga(t‐Bu₂)P(SiMe₃)₂ ( 6 ) and dmap?AlMe₂Cl ( 3 ). 2 – 8 were characterized by NMR spectroscopy, 2 and 6 also by single crystal X‐ray diffraction.     

Synthese,NMR‐Spektren und Molekülstruktur von [(CH3)2Ga{μ‐P(H)Si(CH3)3}2Ga(CH3)2{μ‐P(Si(CH3)3)2}Ga(CH3)2]

Synthesis, NMR Spectra and Structure of [(CH₃)₂Ga{μ‐P(H)Si(CH₃)₃}₂Ga(CH₃)₂{μ‐P(Si(CH₃)₃)₂}Ga(CH₃)₂] The title compound has been prepared in good yield by the reaction of [Me₂GaOMe]₃ (Me = CH₃) with HP(SiMe₃)₂ in toluene (ratio 1 : 1,1) and purified by crystallization from pentane or toluene, respectively. This organogallium compound forms (Ga–P)₃ ring skeletons with one Ga–P(SiMe₃)₂–Ga and two Ga–P(H)SiMe₃–Ga bridges and crystallizes in the monoclinic space group C2/c. The known homologous Al‐compound is isotypic, both (M^III–P)₃ heterocycles have twist‐conformations, the ligands of the monophosphane bridges have trans arrangements.     

Synthese und Struktur von N,N,N‴,N‴‐Tetraisobutyl‐N′,N″‐isophthaloylbis(thioharnstoff) und Dimethanol‐bis(N,N,N‴,N‴‐tetraisobutyl‐N′,N″‐isophthaloylbis(thioureato))dicobalt(II)

Synthesis and Structure of N,N,N?,N?‐Tetraisobutyl‐N′,N″‐isophthaloylbis(thiourea) and Dimethanol‐bis(N,N,N?,N?‐tetraisobutyl‐N′,N″‐isophthaloylbis(thioureato))dicobalt(II) The synthesis and the crystal structure of the ligand N,N,N?,N?‐tetraisobutyl‐N′,N″‐isophthaloylbis(thiourea) and its Co^II‐complex are reported. The ligand co‐ordinates quadridentately forming a di‐bischelate. The donor atoms O and S are arranged in cis‐position around the central Co^II ions. In addition the co‐ordination geometry is determined by methanol molecules resulting in the co‐ordination number five. The complex crystallizes in the space group P1 (Z = 1) with two additional methanol molecules per formula unit. The free ligand crystallizes in the space group P1 (Z = 2) with one methanol molecule per formula unit. It shows the typical keto form of N‐acylthioureas with a protonated central N atom. The structures of both acylthiourea fragments come close to E,Z′‐configurations.     

Umsetzungen der Dielementverbindungen R2E–ER2 [E = Ga,In; R = CH(SiMe3)2] mit Lithium‐phenylethinid – Bildung von Addukten unter Erhalt der E–E‐Bindungen

Reactions of the Dielement Compounds R₂E–ER₂ [E = Ga, In; R = CH(SiMe₃)₂] with Lithium Phenylethynide – Formation of Adducts by Retention of the E–E Bonds Lithium phenylethynide reacted with the dielement compounds tetrakis[bis(trimethylsilyl)methyl]digallane(4) ( 2 ) and diindane(4) ( 3 ) as a Lewis‐base and gave by the addition of one ethynido ligand to one of the Lewis‐acidic central atoms the anionic adducts 4 and 5 with intact Ga–Ga and In–In single bonds. Thus, compounds were formed, in which tricoordinated, coordinatively unsaturated Ga or In atoms are neighbored to tetracoordinated, coordinatively saturated ones. The E–E bonds [255.83 pm in 4 (Ga–Ga) and 285.24 pm in 5 (In–In)] are only slightly lengthened compared to those of the starting compounds 2 and 3 . A dynamic behavior with a fast change of the position of the ethynido ligand was observed for both compounds in solution at room temperature.     

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)°.     

Reaktionen des Gallium‐haltigen Heterocyclus [Me2Ga{HNC(Me)}2CCN]

Reactions of the Gallium‐containing Heterocycle [Me₂Ga{HNC(Me)}₂CCN] The reaction of [Me₂Ga{HNC(Me)}₂CCN] ( 1 ) with fac‐[Mo(CO)₃(MeCN)₃] leads after addition of TMEDA to the molybdenum complex fac‐[Mo(CO)₃( 1 )(TMEDA)] ( 2 ). Under identical reaction conditions with fac‐[W(CO)₃(MeCN)₃] only the tetracarbonyle complex [W(CO)₄(TMEDA)] ( 3 ) could be isolated. Treatment of dilithiated 1 with Me₂SiCl₂ or InCl₃ initiate a fragmentation of the skeleton in 1 . Obtained were the salt [Me₂Ga(TMEDA)][Me₂GaCl₂] ( 4 ) and the indium complex [Me₂InCl(TMEDA)] ( 5 ), respectively. 2 — 5 were investigated by spectroscopical and spectrometrical methods as well as by X‐ray structure determinations. According to these 1 occupies a facial site in 2 by donation of the N‐Atom from the NC group in 1 . The molecules 2 are forming a network of hydrogen bonds. In 3 , the TMEDA ligand acts as an intramolecular chelate ligand. In the salt 4 , the cation as well as the anion are coordinated in a distorted tetrahedral environment, while in 5 a distorded trigonal‐bipyramidal coordination‐sphere is present, leading to a elongated In1‐Cl1 distance of 261.74(9) pm.     

Neue mehrkernige Indium–Stickstoff‐Verbindungen – Synthese und Kristallstrukturen von [In4X4(NtBu)4] (X = Cl,Br, I) und [In3Br4(NtBu)(NHtBu)3]

New Polynuclear Indium Nitrogen Compounds – Synthesis and Crystal Structures of [In₄X₄(N^tBu)₄] (X = Cl, Br, I) and [In₃Br₄(N^tBu)(NH^tBu)₃] The reaction of the indium trihalides InX₃ (X = Cl, Br, I) with LiNH^tBu in THF leads to the In₄N₄‐heterocubanes [In₄X₄(N^tBu)₄] (X = Cl 1 , Br 2 , I 3 ). Additionally [In₃Br₄(N^tBu)(NH^tBu)₃] ( 4 ) was obtained as a by‐product in the synthesis of 2 . 1 – 4 have been characterized by x‐ray crystal structure analysis. 1 – 3 consist of In₄N₄ heterocubane cores with an alternating arrangement of In and N atoms. The In atoms are coordinated nearly tetrahedrally by three N‐atoms and a terminal halogen atom. 4 contains a tricyclic In₃N₄ core which can be formally derived from an In₄N₄‐heterocubane by removing one In atom.     

μ‐{N,N′‐Bis[2‐(dimethyl­amino)ethyl]oxamidato(2–)}‐1κ2O,O′:2κ4N,N′,N′′,N′′′‐bis­(4,4′‐dimethyl‐2,2′‐bipyridine‐1κ2N,N′)dinickel(II) bis­(perchlorate)

In the crystal structure of the title complex, [Ni₂(C₁₀H₂₀N₄O₂)(C₁₂H₁₂N₂)₂](ClO₄)₂ or [Ni(dmaeoxd)Ni(dmbp)₂](ClO₄)₂ {H₂dmaeoxd is N,N′‐bis­[2‐(dimethyl­amino)ethyl]oxamide and dmbp is 4,4′‐dimethyl‐2,2′‐bipyridine}, the deprotonated dmaeoxd²⁻ ligand is in a cis conformation and bridges two Ni^II atoms, one of which is located in a slightly distorted square‐planar environment, while the other is in an irregular octa­hedral environment. The cation is located on a twofold symmetry axis running through both Ni atoms. The dmaeoxd²⁻ ligands inter­act with each other via C—H⋯O hydrogen bonds and π–π inter­actions, which results in an extended chain along the c axis.     

Die Kristallstruktur von cis‐ und trans‐N‐iso‐Propylamidodimethylindium, [(CH3)2In‐N(H)iC3H7]2

The Crystal Structure of cis‐ and trans‐N‐iso‐Propylamidodimethyl Indium, [(CH₃)₂In‐N(H)ⁱC₃H₇]₂ According to the X‐ray structure determination [(CH₃)₂In‐N(H)ⁱC₃H₇]₂ (prepared from InMe₃ (Me = CH₃) and H₂NⁱPr (ⁱPr = CH(CH₃)₂) crystallizes in the monoclinic space group P2₁/n with 3 dimeric trans as well as 3 dimeric cis isomers per unit cell. The centrosymmetric form has a planar In₂N₂ core with In—N bonds of 222.1(4) and 222.9(5) pm, respectively, the skeleton of the cis isomer with In—N bonds of 221.4(4) pm is slightly folded (13.7°). Some ¹H, ¹³C NMR, IR, and Raman data are reported.     

Bis(2,2′‐bipyridyl‐N,N′)­tris­(nitrato‐O,O′)­neodymium

The title compound, [Nd(bipy‐N,N′)₂(NO₃–O,O′)₃], is found to be isomorphous with the La and Lu analogues having three bidentate nitrate and two bipyridyl ligands giving a ten co‐ordinate environment.     

Darstellung,Charakterisierung und Reaktionsverhalten von Natrium‐ und Kaliumhydridosilylamiden R2(H)Si—N(M)R′ (M = Na,K) — Kristallstruktur von [(Me3C)2(H)Si—N(K)SiMe3]2·THF

Preparation, Characterization and Reaction Behaviour of Sodium and Potassium Hydridosilylamides R₂(H)Si—N(M)R′ (M = Na, K) — Crystal Structure of [(Me₃C)₂(H)Si—N(K)SiMe₃]₂ · THF The alkali metal hydridosilylamides R₂(H)Si—N(M)R′ 1a‐Na — 1d—Na and 1a‐K — 1d‐K ( a : R = Me, R′ = CMe₃; b : R = Me, R′ = SiMe₃; c : R = Me, R′ = Si(H)Me₂; d : R = CMe₃, R′= SiMe₃) have been prepared by reaction of the corresponding hydridosilylamines 1a — 1d with alkali metal M (M = Na, K) in presence of styrene or with alkali metal hydrides MH (M = Na, K). With NaNH₂ in toluene Me₂(H)Si—NHCMe₃ ( 1a ) reacted not under metalation but under nucleophilic substitution of the H(Si) atom to give Me₂(NaNH)Si—NHCMe₃ ( 5 ). In the reaction of Me₂(H)Si—NHSiMe₃ ( 1b ) with NaNH₂ intoluene a mixture of Me₂(NaNH)Si—NHSiMe₃ and Me₂(H)Si—N(Na)SiMe₃ ( 1b‐Na ) was obtained. The hydridosilylamides have been characterized spectroscopically. The spectroscopic data of these amides and of the corresponding lithium derivatives are discussed. The ²⁹Si‐NMR‐chemical shifts and the ²⁹Si—¹H coupling constants of homologous alkali metal hydridosilylamides R₂(H)Si—N(M)R′ (M = Li, Na, K) are depending on the alkali metal. With increasing of the ionic character of the M—N bond M = K > Na > Li the ²⁹Si‐NMR‐signals are shifted upfield and the ²⁹Si—¹H coupling constants except for compounds (Me₃C)(H)Si—N(M)SiMe₃ are decreased. The reaction behaviour of the amides 1a‐Na — 1c‐Na and 1a‐K — 1c‐K was investigated toward chlorotrimethylsilane in tetrahydrofuran (THF) and in n‐pentane. In THF the amides produced just like the analogous lithium amides the corresponding N‐silylation products Me₂(H)Si—N(SiMe₃)R′ ( 2a — 2c ) in high yields. The reaction of the sodium amides with chlorotrimethylsilane in nonpolar solvent n‐pentane produced from 1a‐Na the cyclodisilazane [Me₂Si—NCMe₃]₂ ( 8a ), from 1b‐Na and 1‐Na mixtures of cyclodisilazane [Me₂Si—NR′]₂ ( 8b , 8c ) and N‐silylation product 2b , 2c . In contrast to 1b‐Na and 1c‐Na and to the analogous lithium amides the reaction of 1b‐K and 1c‐K with chlorotrimethylsilane afforded the N‐silylation products Me₂(H)Si—N(SiMe₃)R′ ( 2b , 2c ) in high yields. The amide [(Me₃C)₂(H)Si—N(K)SiMe₃]₂·THF ( 9 ) crystallizes in the space group C2/c with Z = 4. The central part of the molecule is a planar four‐membered K₂N₂ ring. One potassium atom is coordinated by two nitrogen atoms and the other one by two nitrogen atoms and one oxygen atom. Furthermore K···H(Si) and K···CH₃ contacts exist in 9 . The K—N distances in the K₂N₂ ring differ marginally.