ISSN:
0044-2313
Keywords:
Tris(trimethylsilyl)methyl-derivatives, Lithium, Aluminium, Gallium, Indium
;
spectra
;
X-ray Structures
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Base-free Tris(trimethylsilyl)methyl Derivatives of Lithium, Aluminium, Gallium, and IndiumBase-free LiR* (R*=-C(SiMe3)3) has been prepared from R*Cl and Li-metal in toluene at 85-90°C and used to synthesize the metallanes R*MMe2 with M = Al, Ga and In, respectively. The NMR (1H, 13C, 29Si) and the vibrational spectra of these trisyl compounds have been discussed.AlCl3 and LiR*(ratio 1 : 1) forms the metallate metallate Li[R*AlCl3]. The triclinic unit cell (space group P1) consists of a centrosymmetric assoziate, formed by four Li[R*AlCl3]- units with Al—Cl…Li bridges, two pairs of Li-atoms differing in their chlorine-coordination and two disordered toluene molecules, inserted in the crystal lattice (R1wR2 =0,0444/0,1072).The reaction of GaCl3 with LiR* (I :1) gives the unusual sesquichloride (R*Ga(Cl1,33)Me0,67)3 in moderate yield. The X-ray structure determination shows a Ga3Cl3-skeleton with chairconformation and disordered, terminal gallium ligands (R1/wR2= 0,0646/0,2270).
Notes:
Basefreies LiR* (R*=-C(SiMe3)3) wurde aus R*Cl und Lithiummetall in Toluol bei 85-90°C erhalten und zur Darstellung der Dimethylmetallane R*MMe2 mit M = Al, Ga, In verwendet, die durch NMR- (1H, 13C, 29Si) und Schwingungsspektren (Raman, IR) charakterisiert werden.AlCl3 und LiR* (Molverhältnis 1 : 1) bilden das Metallat Li[R*AlCl3]. Die trikline Einheitszelle (Raumgruppe P1) enthält ein zentrosymmetrisches, über Al—Cl … Li—Brücken gebildetes Assoziat aus vier Li[R*AlCl3]-Einheiten, mit zwei paarweise unterschiedlich von Chlor koordinierten Li-Atomen sowie zwei fehlgeordnete Toluolmoleküle (R1/ wR2 = 0,0444/0,1072).Die Reaktion von GaCl3 mit LiR* (1 : 1) in Toluol führt in mäßiger Ausbeute zum ungewöhnlichen Sesquichlorid (R*Ga(Cl1,33)Me0,67)3. Die Röntgenstrukturanalyse zeigt ein sesselförmig gewelltes Ga3Cl3-Sechsringgerüst und fehlgeordnete, terminale Liganden am Galliumatom (R1/ wR2 = 0,0646/0,2270).Li[R*AlCl3]. The triclinic unit cell (space group P1) consists of a centrosymmetric assoziate, formed by four Li[R*AlCl3]-units with Al-Cl … Li bridges, two pairs of Li-atoms differing in their chlorine-coordination and two disordered toluene molecules, inserted in the crystal lattice (R1/wR2 = 0,0444/0,1072).The reaction of GaCl3 with LiR* (1 : 1) gives the unusual sesquichloride (R*Ga(Cl1,33)Me0,67)3 in moderate yield. The X-ray structure determination shows a Ga3Cl3-skeleton with chairconformation and disordered, terminal gallium ligands (R1/wR2 = 0,0646/0,2270).
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19976230922
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