Die Kristallstruktur von (CH3)2GaC5H5

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Abstract

Dimethyl(cyclopentadienyl gallium, (CH3)2GaC5H5, crystallizes with monoclinic symmetry in space group P21/c; the cell dimensions are a = 6.587(3), b = 9.154(3), c = 12.756(5) Å and β = 113.20(3)o with Z = 4. The structure was solved using heavy atom techniques and refined by least-squares techniques to give a value of R = 0.046 for the 1719 observed reflections. The structure consists of chains of dimethylgallium-groups bridged by cyclopentadienyl rings along the b-axis. Each gallium atom has a distorted tetrahedral environment with Ga-methyl distances of 1.965 Å and Ga-Cp distances of 2.215 and 2.314 Å, respectively.

Zusammenfassung

Dimethyl(cyclopentadienyl) gallium, (CH3)2GaC5H5, kristallisiert monoklin in der Raumgruppe P21/c mit den Gitterkonstanten a = 6,587(3), b = 9,154(3), c = 12,756 Å, β = 113,20(3)o mit Z = 4. Die Struktur wurde aus Patterson-, Fourier- und Differenz-Fourier-Synthesen abgeleitet und nach der Methode der kleinsten Fehlerquadrate bis zu einem R-Wert von 0,046 bei 1719 beobachteten Reflexen verfeinert. Die struktur besteht aus Ketten von Dimethylgalliumgruppen, die entlang der b-Achse durch Cyclopentadienylringe verbrückt sind. Die Galliumatome befinden sich dabei in verzerrt tetraedrischer Umgebung mit Ga-Methylabständen von 1,965 Å und Ga-Cp-Abständen von 2,215 bzw. 2,314 Å.

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    Lack of solubility of the s-block compounds of Cp− in suitable inert solvents and their extreme reactivity likely discouraged detailed earlier structural investigations on these salts. Such efforts were not begun in earnest until the 1970s when the first reports on systematic studies of main-group cyclopentadienides and related anions appeared in the literature [7–21]. In the intervening years research on both s- and p-block cyclopentadienides grew exponentially as the result of numerous synthetic-structural [22–48] and computational studies [49–52].

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