Z. Naturforsch. 51 b, 637-645 (1996); eingegangen am 14. September 1995 Gallium Compounds, Indium Compound, Crystal Structure (PhCH2)2GaBr (1) can be obtained by the redistribution reaction of GaBr3 with Ga(CH2Ph)3 in a molar ratio 1:2. Treatment of 1 or (PhCH2)2GaCl with one equivalent of LiN(H)/-Bu gives the diorganogallium amide [(PhCH2)2GaN(H)r-Bu]2 (2). The toluene-insoluble PhCH2InCl2 can be structurally investigated after dissolving in THF and crystallization as [PhCH2InCl2(THF)2] (3). 1 3 were characterized with NMR, IR and MS techniques as well as by X-ray structure determinations. 1 forms two crystallographic independent dimers while 2 is a centrosymmetric dimer in the solid state. 3 is a monomer with a trigonal-bipyramidal coordination sphere at the indium center.

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)(3)C6H2) 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)(2)GaTe(t-Bu)](2) with CsF in THF. The triorganofluoro gallate [Cs{(PhCH2)(3)GaF}](2) (3) was isolated. The triorganofluoro gallate Cs[Me3GaF] does not react with dry O-2 in THF. With S-8 in THF a reaction was achieved and the diorganodifluoro gallate [Cs(THF)(0.5)(Me2GaF2)] (4) could be characterized. The treatment of MesInBr(2) with CsF in acetonitrile gives as only identified compound the indate Cs[MesInBr(3)] (5).

The organogallium arsenide [Pri(Cl)GaAsBu2t]2 (1) and the organoindium arsenide [(PhCH2)2 InAsBu2t]2 (2) have been prepared by the reaction of the corresponding halides PriGaCl2 and (PhCH2)2InCl with Bu2tAsLi in THF and Et2O, respectively. 1 and 2 have been fully characterized by elemental analysis and IR, NMR, and MS techniques as well as by X-ray diffraction. According to cryoscopic molecular weight determinations in benzene, 1 and 2 are present as dimers in solution. The structures of 1 and 2 display rhombic distorted four-membered rings M2As2 (M = Ga, In).

Cs[i-Bu3AlF] (1) kann durch die Reaktion von Al(i-Bu)3 mit CsF in Toluol erhalten werden. Bei einer Halogenaustauschreaktion von Mes*GaCl2 mit CsF in Acetonitril bildete sich nicht das gewünschte Mes*GaF2 (Mes* = 2,4,6-(t-Bu)3C6H2), sondern es wurde durch zusätzliche Addition einer Einheit CsF das Metallat Cs[Mes*GaF3] (2) isoliert. Eine Ligandendistribution wird bei der Einwirkung von CsF auf [(PhCH2)2GaTe(t-Bu)]2 in THF beobachtet, wobei das Triorganofluorogallat [Cs{(PhCH2)3GaF}]2 (3) gefunden wurde. Das Triorganofluorogallat Cs[Me3GaF] reagiert in THF nicht mit trockenem O2. Eine Umsetzung wurde mit S8 erzielt. Dabei konnte das Diorganodifluorogallat [Cs(THF)0,5(Me2GaF2)] (4) charakterisiert werden. Die Behandlung von MesInBr2 mit CsF in Acetonitril liefert als einzige identifizierte Verbindung das Indat Cs[MesInBr3] (5). 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).

AbstractDifluorenylzink (Fluorenyl = Fl) ergibt mit AlCl3 in THF das Komplexsalz [AlCl2(THF)4][ZnCl3(THF)] (1), während die gleiche Reaktion mit GaCl3 zum THF‐stabilisierten Gallan [GaFl3(THF)] (2) führt. Aus Umsetzungen mit InCl3 und TlCl3 konnte bisher nur der Komplex [InCl3(THF)3] (3) isoliert werden. Das Lösungsmittelgemisch THF/DME liefert den Komplex [InCl3(DME)(THF)] (4). Für einen Bindungslängenvergleich mit dem Zinkat‐Ion [ZnCl3(THF)]− wurde der Komplex [ZnCl2(THF)2] (5) dargestellt. 1‐5 wurden mittels NMR‐ und IR‐Spektroskopie untersucht. Von 1, 2 · Toluol, 3 und 5 konnte eine Röntgenstrukturanalyse angefertigt werden. 1 besitzt danach ein Kation mit linearer AlCl2‐Einheit und ein Zinkat‐Ion, das durch den THF‐Liganden nur wenig pyramidalisiert ist. In 2 liegt ebenfalls ein verzerrt tetraedrisch koordiniertes Metall‐zentrum vor. Für 3 wurde eine meridionale Anordnung der THF‐Liganden gefunden. In 5 wirkt sich die Abwesenheit einer Ladung im Vergleich zum Zinkat‐Ion [ZnCl3THF]− deutlich bindungsverkürzend aus.

Difluorenyl zinc (fluorenyl = Fl) gives with AlCl3 in THF the salt [AlCl2(THF)(4)][ZnCl3(THF)] (1) while the corresponding reaction with GaCl3 leads to the THF stabilized gallane [GaFl(3)(THF)] (2). As a result of the reactions of InCl3 and TlCl3 by the mentioned way above only the complex [InCl3(THF)(3)] (3) could be isolated. The mixture of solvents DME/THF gives the complex [InCl3(DME)(THF)] (4). For a comparison of the binding parameters with the zincate ion [ZnCl3(THF)](-) the compound [ZnCl2(THF)(2)] (5) has been synthesized. 1-5 were characterized by NMR and IR techniques. 1, 2 toluene, 3 and 5 could also be investigated by X-ray structure analysis. According this, 1 possesses a cation with a linear AlCl2 unit and a zincate ion, which is only sligthly pyramidalisized by the THF ligand. 2 contains also a distorted tetrahedral coordinated metal center. For 3 a meridional arrangement of the THF ligands was found. In 5 the absence of a negative charge leads to a shortening of the bond lengths in comparison to the zincate ion [ZnCl3(THF)](-).

The reaction of TlCl3 with MesMgBr (Mes = 2,4,6-Me(3)C(6)H(2)) in THF at 0 degrees C gives trimesitylthallium, TlMes(3) (2). 2 has been characterized with NMR, IR and MS techniques as well as by an X-ray structure determination. 2 crystallizes isostructural to InMes(3) (1a). The molecules of 2 are coordinated by the three mesityl substutients in a planar fashion. A new modification of InMes(3) (1b) could be obtained by recrystallization of InMes(3) from toluene/n-pentane in the space group C2/c. The literature known modification la and the new metallane 2 crystallize in the space group P2(1)/n. The molecules in 1b possess C-2-symmetry. The trimesitylelement compounds EMes(3) (E = B, Al, Ga, In, Tl) have been compared with each other.

(PhCH(2))(2)GaBr (1) can be obtained by the redistribution reaction of GaBr3 with Ga(CH(2)Ph)(3) in a molar ratio 1:2. Treatment of 1 or (PhCH(2))(2)GaCl with one equivalent of LiN(H)t-Bu gives the diorganogallium amide [(PhCH(2))(2)GaN(H)t-Bu](2) (2). The toluene-insoluble PhCH(2)InCl(2) can be structurally investigated after dissolving in THF and crystallization as [PhCH(2)InCl(2)(THF)(2)] (3). 1 - 3 were characterized with NMR, IR and MS techniques as well as by X-ray structure determinations. 1 forms two crystallographic independent dimers while 2 is a centrosymmetric dimer in the solid state. 3 is a monomer with a trigonal-bipyramidal coordination sphere at the indium center.

(PhCH2)2GaBr (1) can be obtained by the redistribution reaction of GaBr3 with Ga(CH2Ph)3 in a molar ratio 1:2. Treatment of 1 or (PhCH2)2GaCl with one equivalent of LiN(H)t-Bu gives the diorganogallium amide [(PhCH2)2GaN(H)t-Bu]2 (2). The toluene-insoluble PhCH2InCl2 can be structurally investigated after dissolving in THF and crystallization as [PhCH2InCl2(THF)2] (3). 1 - 3 were characterized with NMR, IR and MS techniques as well as by X-ray structure determinations. 1 forms two crystallographic independent dimers while 2 is a centrosymmetric dimer in the solid state. 3 is a monomer with a trigonal-bipyramidal coordination sphere at the indium center.

The cesium triorganofluorometalates [Cs{R(3)MF}](4) (1, M = Ga, R = Et; 2, M = Ga, R = i-Pr; 3, M = In, R = Et; 4, M = in, R = i-Pr) have been prepared by the reaction of the corresponding group 13 metallanes GaEt(3), Ga(i-Pr)(3), InEt(3), and In(i-Pr)(3) with CsF in acetonitrile. 1-4 have been fully characterized by elemental analysis, and IR, NMR, and MS techniques. The crystal structures of 2 and 4 have been determined. 2 and 4 are isostructural and crystallize in the cubic space group I23, with a = 1396.3(1) pm, V = 2722.3(5) x 10(6) pm(3), Z = 2, and R(1) = 0.0168 (wR(2) = 0.0343) for 2 and a 1417.1(2) pm, V = 2845.8(6) x 10(6) pm(3), Z = 2, and R(1) = 0.0166 (wR(2) = 0.0354) for 4. The structures of 2 and 4 display strongly distorted cubes with alternating cesium and fluorine atoms and can be described as (CsF)(4) subunits of the CsF structure stabilized by M(i-Pr)(3) groups. According to the analytical and spectroscopic data, 1 and 3 also possess Cs-F heterocubane structure.

The reaction of MMes(3) (M = Ga, In; Mes = 2,4,6-Me(3)C(6)H(2)) with CsF in acetonitrile yields the trimesitylfluorometalates [{Cs(MeCN)(2)}{Mes(3)MF}](2) . 2MeCN([1](2) . 6MeCN, M = Ga; [2](2) . 6MeCN, M = In). Ga(CH(2)Ph)(3) gives with CsF under the same conditions the salt [Cs{(PhCH(2))(3)GaF}](2) . 2MeCN ([3](2) . 2MeCN). The treatment of 1 equiv CsF with 2 equiv of GaMes(3) does not lead to Cs[Mes(3)GaFGaMes(3)] but to [1](2) . 6MeCN and the adduct [Mes(3)Ga(MeCN)] (4). [1](2) . 6MeCN-4 have been characterized by NMR, IR, and MS techniques as well as by X-ray analyses. [1](2) . 6MeCN and [2](2) . 6MeCN are solvated ion pairs in acetonitrile, while [3](2) . 2MeCN shows a monomer-dimer equilibrium. According to the X-ray structure determinations, [1](2) . 6MeCN and [2](2) . 6MeCN are isostructural and contain Cs-F four-membered rings. The fluorine centers at the rings are bound to the metallane groups. Each cesium cation is coordinated by two molecules of acetonitrile and by one mesityl group in a eta(3)-fashion. The basic structural feature of [3](2) . 2MeCN is also a Cs-F four-membered ring; however, the cations in [3](2) . 2MeCN are surrounded by three phenyl groups of the benzyl substituents. The three eta(6)-bound phenyl rings are contributed from two different metallane units. 4 possesses a distorted tetrahedral coordination sphere with a low pyramidalization of the Ga center (angular sum: 355 degrees).

Cesium‐Fluorine Four‐Membered Rings as Structural Motive in Cesium Triorganofluoro Metalates of Group 13The reactions of AlMe3, GaMe3, and InMe3 with CsF in acetonitrile furnish the corresponding trimethylfluoro metalates Cs[Me3MF] (1: M = Al, 2: M = Ga, 3: M = In). The salt‐like compounds 1 – 3 were characterized by NMR, IR, and MS techniques as well as by X‐ray structure analysis. Cs2F2 four‐membered rings are the structure‐dominating units in all three compounds. Compound 1 consists of puckered layers of weakly associated Cs2F2 rings parallel to (100), while the four‐membered rings in 2 form infinite ladder‐type chains. The Cs–F rings in 3 build up a heterocubane with a Cs4F4 core by ring stacking.

The reaction of i-Pr2InCl and (PhCH(2))(2)InCl with LiPPh(2) in Et(2)P/THF or Et(2)O/n-pentane gives the organoindium phosphides i-Pr(2)InPPh(2) (1) and (PhCH(2))(2)InPPh(2) (2), respectively. The tetrameric compound [MesInPMes](4) (3) has been prepared by the treatment of MesInCl(2) with MesPLi(2) Et(2)O. 1-3 have been characterized by NMR, IR, and MS techniques as well as by X-ray diffraction. According to cryoscopic molecular weight determinations in benzene, 1 and 2 are present as a monomer-dimer equilibrium mixture, while 3 is tetrameric in solution. The X-ray analyses of 1 and 2 confirm the existence in the solid state of trimers in [i-Pr(2)InPPh(2)](3) and [(PhCH(2))(2)InPPh(2)](3) . OEt(2) with distorted In3P3 six-membered rings in boat conformations. According to its structural characterization [MesInPMes]4 . 4.5THF is a heterocubane with an In4P4 core shielded by the bulky organic groups.

i-Pr3In gives with InBr3 (molar ratio 2:1, toluene, 50 degrees C) i-Pr2InBr (1) and (molar ratio 1:2, toluene, 80 degrees C) i-PrInBr2 (2). The corresponding reaction of (PhCH(2))(3)In and InBr3 (2:1) gives (PhCH(2))(2)InBr (3), while PhCH(2)InBr(2) could be isolated only as ether adduct [PhCH(2)InBr(2)(OEt(2))(n)] (4). With DME/MeCN and 2 and 4 with THF, respectively, yields the solvate complexes [InBr3(DME)(MeCN)] (5), [i-PrInBr2(THF)(2)] (6) and [PhCH(2)InBr(2)(THF)(2)] (7). The compounds 1-7 were investigated with NMR-, IR- and MS-techniques. Pyrolysis of the raw material of i-Pr3In, which contains ''MgBrCl'' and additional treatment with Et(2)O yields the salt [Mg3Cl4,65Br0,35(Et(2)O)(6)][[i-PrInBr2,7Cl0,3] (8). The cation, a trinuclear magnesium complex, possesses local D-3h-symmetrie of the Mg(1)X(5) backbone (X = Cl, Br).

The title compound 1 was synthesized by the reaction of LiCl with TMEDA (N,N,N',N'-tetramethylethylendiamine) and water at 120 degrees C in boiling TMEDA. 1 was crystallized at -30 degrees C as colorless crystals and characterized by NMR and IR spectroscopy as well as by an X-ray structure determination. 1 is a polymer in the solid state, built up by an alternating arrangement of stick-like tetranuclear Li complexes and two TMEDA molecules. The complexes and the TMEDA molecules are connected by hydrogen bridges in infinite chains.

Abstract The title compound 1 was synthesized by the reaction of LiCl with TM EDA (N,N,N′,N′- tetramethylethylendiamine) and water at 120 °C in boiling TM EDA. 1 was crystallized at - 30 °C as colorless crystals and characterized by NMR and IR spectroscopy as well as by an X-ray structure determination. 1 is a polymer in the solid state, built up by an alternating arrangement of stick-like tetranuclear Li complexes and two TMEDA molecules. The complexes and the TMEDA molecules are connected by hydrogen bridges in infinite chains.