The product is a light-to dark-brown solid depending on its grain size; it is sensitive to moisture and is practically insoluble in all the common organic solvents. In contrast to the nitrosyl chlorides of iron [ l ] and cobalt [2], the new compound cannot be sublimed and is therefore probably polymeric in nature. Its infrared spectrum in Nujol contains N-0 absorptions at 1924 (s), 1761 (vs) cm-1 [3] plus two bands at 309 and 261 cm-1 which can be assigned to V-CI stretching vibrations. Comparison of the infrared spectrum with those of other nitrosylmetal chlorides [3] showed that [V(N0)3C12In has probably a polynuclear structure (1) with terminal a n d bridging chloro ligands. This structure contains sixfold coordinated vanadium with an inert-gas configuration 45.5 35/1 [a1 16.5 34-35/3 16.0 57-5813 40.0 [b] 45/1.5 [a]and has a trigonal bipyramidal arrangement of the N O groups; these features are in agreement with the fact that the compound is diamagnetic and gives only two N -0 absorptions in the infrared. Received: December 15th, 1964 [Z 880/701 IE] German version: Angew. Chem. 77, 134 (1965) [I] W.Trimethylsilane reacts a t -20 O C with equimolar amounts of gallium trichloride to form trimethylchlorosilane (99.5 "/: yield) and pure dichlorogallane.(H3C)3SiH + GaC13 + (H3C)3SiCI + HGaC12When the chlorosilane is pumped off at -30 OC, a residue of HGaC12 is obtained in 95 % yield as colorless crystals which dissolve well and without decomposition a t low temperatures in anhydrous solvents such as benzene, cyclohexane, or diethyl ether [l].

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Low molecular-weight model substances of well-defined composition were prepared for the first time in connection with an investigation of the principles of structure and bonding in heterosiloxanes. Examples of such compounds are RiSiOXR:, (RiSi0)2XR$ (R:Si0)3XR2, and (RiSi0)dX. where X = Si, Ge, Sn, or Pb, R1 = CH3 or CzHs, and R2 = CH3, C2H5, etc. Specific heterolytic cleavage reactions with Lewis acids or nucleophilic reagents, as well as infrared and N M R

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