- Synthesis and structures of C60 fullerene chlorides
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Systematic study of chlorination of fullerene C60 with inorganic chlorides SbCl5, VCl4, MoCl5, and KICl 4 was carried out. Higher chlorofullerenes, viz., T h-C60Cl24, C60Cl28, C2-C60Cl30, and D3d-C 60Cl30, can be prepared depending on the temperature and time of chlorination. The molecular and crystal structures of C 60Cl24·VOCl3, C60Cl 30·2CS2, and C60Cl30O 1.22 were determined by single-crystal X-ray diffraction. Fullerenes C60Cl28 and C2-C60Cl30 were shown to be only kinetically stable, whereas D3d-C 60Cl30 is a thermodynamically stable product. Transformations of less chlorinated fullerenes into more chlorinated products are accompanied by substantial changes in the addition patterns.
- Troyanov,Shustova,Popov,Sidorov
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- New details concerning the reactions of nitric oxide with vanadium tetrachloride
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The slow addition of NO to a CCl4 solution of VCl4 reproducibly forms the known polymer [V(NO)3Cl2 ]n as a dark brown powder. Treatment of a CH2Cl 2 suspension of [V(NO)3Cl2]n with excess THF generates mer-(THF)3V(NO)Cl2 (1) which can be isolated as an orange crystalline material in 55% yield. The reaction of 1 with excess MeCN or 1 equiv of trimpsi (trimpsi = tBuSi(CH 2PMe2)3) provides yellow-orange (MeCN) 3V(NO)Cl2·MeCN (2·MeCN) and yellow (trimpsi)V(NO)Cl2 (3), respectively. A black, crystalline complex formulated as [NO][VCl5] (4) is formed by the slow addition of NO to neat VCl4 or by the reaction of excess CINO with neat VCl 4. Complex 4 is extremely air- and moisture-sensitive, and IR spectroscopy suggests that in solutions and in the gas phase it dissociates back into VCl4 and CINO. Reaction of 4 with excess [NEt 3(CH2Ph)]CI generates [NEt3(CH 2Ph)]2[VCl6]·2CH2Cl 2 (5·2CH2Cl2), which can be isolated as deep-red crystals in 51% yield. All new complexes have been characterized by conventional spectroscopic methods, and the solid-state molecular structures of 1, 2·MeCN, and 5·2CH2Cl2 have been established by single-crystal X-ray diffraction analyses.
- Hayton, Trevor W.,Patrick, Brian O.,Legzdins, Peter
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p. 7227 - 7233
(2008/10/09)
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- Chlorination of C60 and C70 fullerenes using SbCl5 and VCl4 chlorides
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Fullerenes C60 and C70 are reacted with variable-valence element chlorides (SbCl5 or VCl4) in glass ampoules at 160-180°C to yield chlorides C60Cl24 and C70Cl28, respectively. The products are characterized using elemental analysis, IR spectroscopy, and thermal analysis. The use of C60Br24 or C70Br10 instead of C 60 or C70 in the reactions with SbCl5 substantially shortens the reaction time. It is for the first time that a high degree of chlorination (C70Cl28) of fullerene C 70 against the literature data (C70Cl10) has been achieved.
- Troyanov,Shustova,Popov,Feist,Kemnitz
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p. 1303 - 1307
(2008/10/09)
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- Molecular shapes of the first row transition element dichlorides with particular reference to vanadium dichloride
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In contrast to conclusions from gas phase electron diffraction, infrared studies of vanadium dichloride in argon matrices can be satisfactorily interpreted in terms of a linear molecule. The nature of the species above heated vanadium dichloride has been investigated using mass spectroscopy and chemical analyses of both sublimate and residue. As with TiCl2, TiCl3, and CrCl3, it appears that disproportionation reactions can occur for VCl2. The nature of the products is dependent on the vaporization conditions.
- Beattie,Jones,Willson,Young
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- SYNTHESIS AND PROPERTIES OF COVALENT TRI- AND TETRAVALENT VANADIUM
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Reactions of VCl3*3THF with RMgX (R = Ph, CH2SiMe3, C6F5) in various ratios have been studied.The stable compounds R3V*THF (R = CH2SiMe3, C6F5) were obtained.The chemical properties of R3V*THF, R4V*2L (R = CH2Ph, L = Et2O; R = C6F5, L = THF) and (Me3SiCH2)4V were investigated.Cleavage of the vanadium-carbonium ?-bond occurs in reactions with H2O, HCl and HgCl2.The insertion of carbon dioxide into the vanadium-carbon ?-bond was investigated.A scheme for the derivatives of tri- and tetravalent vanadium is proposed.Oxidative addition to (C6F5)3V*THF by Ph3CCl and VCl3*3THF was also studied.
- Razuvaev, G.A.,Latyaeva, V.N.,Vyshinskaya, L.I.,Drobotenko, V.V.
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p. 169 - 182
(2007/10/02)
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- The Preparation of Vanadium Tetrachloride from Vanadium Dichloride Oxide and Vanadium Trichloride and the Hydrogen Reduction Process of Vanadium Tetrachloride
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The reactions of VCl2O and VCl3 with chlorine, and the reaction of VCl3O, formed by the chlorination of VCL2O, with chlorine in the presence of carbon were examined.The products formed by the reaction between gaseous VCl4 and hydrogen at various temperatures, and the behavior of VCl3 and VCl2 on heating in a hydrogen stream were examined.The reaction between VCl2O and chlorine occurs above ca. 120 deg C and proceeds markedly above ca. 170 deg C to form VCl3O.VCl4 can be obtained by passing the gaseous VCl3O together with chlorine through a carbon bed held at ca. 700 deg C.The reaction between VCl3 and chlorine occurs above ca. 80 deg C and proceeds markedly above ca. 170 deg C to form VCl4.The hydrogen reduction process of VCl4 in the vapor phase may be represented as follows: The reaction between VCl4 and hydrogen, 2VCl4(g) + H2(g) -> 2VCl3(s) + 2HCl(g), proceeds above ca. 500 deg C to form VCl3.Subsequently, the hydrogen reduction of the VCl3, 2VCl3(s) + H2(g) -> 2VCl2(s) + 2HCl(g), and the disproportionation of the VCl3, 2VCl3(s) -> VCl4(g), proceed to form VCl2.Above ca. 620 deg C, the reaction between the VCl2 and hydrogen, VCl2(s) + H2(g) -> V(s) + 2HCl(g), proceeds to form vanadium.
- Yajima, Akimasa,Matsuzaki, Ryoko,Saeki, Yuzo
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p. 2843 - 2846
(2007/10/02)
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