The reaction of MMes3 (M = Ga, In; Mes = 2,4,6-Me3C6H2) with CsF in acetonitrile yields the trimesitylfluorometalates [{Cs(MeCN)2}{Mes3MF}]2·2MeCN ([1]2·6MeCN, M = Ga; [2]2· 6MeCN, M = In). Ga(CH2Ph)3 gives with CsF under the same conditions the salt [Cs{(PhCH2)3GaF}]2·2MeCN ([3]2·2MeCN). The treatment of 1 equiv CsF with 2 equiv of GaMes3 does not lead to Cs[Mes3GaFGaMes3] but to [1]2·6MeCN and the adduct [Mes3Ga(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 η3-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 η6-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°).

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The reaction of GaMe3 in acetonitrile in the presence of halide ions, F-, Cl-, and Br-, at 60 °C gives the heterocycle [Me2Ga{HNC(Me)}2C(CN)] (1). Further reaction with GaMe3 and MeCN leads to a hexanuclear gallium complex [(Me2Ga)4(MeGa)2{HNC(Me)C(CN)CH(NCMe)2}2] (2). In addition to 2, 2·3MeCN and 2·2GaMe3 can be obtained under special conditions. 1 and 2 have been characterized by their NMR, IR, and MS spectra. X-ray analyses were performed with 1, 2, 2·3MeCN, and 2·2GaMe3. Compound 1 consists of six-membered heterocycles, which are connected by hydrogen bridges to zigzag chains along the direction [010]. 2 contains 10 units of acetonitrile and six gallium centers forming a centrosymmetric eight-membered Ga−N ring. The structure of 2·3MeCN exhibits two hydrogen-bridged MeCN molecules and one acetonitrile molecule which is not connected to another component of the unit cell. In 2·2GaMe3 two units of GaMe3 are coordinated to the CN groups of 2 creating weakly pyramidalized GaMe3 fragments.

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Abstract:The reaction of CsCl with In(CH,Ph), yields the triorganochloroindate Cs [(PhCH,),InCI] ( 1 ) . Treatment of In(CH2Ph), with dry 0, gives the alkoxide, whcrcas the reaction of 1 with O2 leads to Keywords CS,[O{P~CH,I~(OCH,P~),)~] ( 3 ) . According to X-ray structural investigations, 1 concesium -indium * layered comtains Cs,CI, four-mcmbered rings as basic structural motif. The dirners are connected pounds a metalla(crown ethers) a by Cs-7c-electron interactions to form a layer structure. Compound 3 can be described as a metalla(crown ether) fragment coordinating two Cs' ions. Additional shielding of the Cs centers by weak Cs-n-electron contacts was observed.pi interactions