Preparation and Properties of New Cationic Dienyl-isonitrile-dicarbonyl Complexes of Iron and Ruthenium The hydride abstraction from the η4-diene isonitrile metal dicarbonyls M(η4-dien)(CNR)(CO)2 (M = Fe, Ru; dien = C6H8 cyclohexadiene-1.3; C7H10 cycloheptadiene-1.3; R = Me, Et) with [Ph3C]BF4 lead to the η5-dienyl isonitrile dicarbonyl metal cations [M(η5-dienyl)(CNR)(CO)2]+ [dienyl = cyclohexa-2.4-dien-1-yl (C6H7), cyclohepta-2.4-dien-1-yl (C7H9)]. [Fe(η5? C8H9)(CNMe)(CO)2]+ (C8H9 = bicyclo[5.1.0]octa-3.5-dien-2-yl) is formed by protonation of Fe(η4? C8H8)(CNMe)(CO)2 (C8H8 = COT) under valency isomerization. The two cations [Fe(η5? C7H9)(CNMe)(CO)2]+ and [Fe(η5? C8H9)(CNMe)(CO)2]+ can be deprotonated with NEt3 to the neutral cycloheptatriene respectively COT complexes Fe(η4? C7H8)(CNMe)(CO)2 and Fe(η4? C8H8)(CNMe)(CO)2. The temperature dependent 13C-NMR spectra of [Fe(η5? C7H9)(CNMe)(CO)2]+ and [Ru(η5? C6H7)(CNMe)(CO)2]+ show the fluctional behaviour of these cations in solution. At low temperatures one CO group occupies the apical position of a square pyramid whereas the isonitrile ligand, the other CO group and the dienyl part are in the basal positions. The ΔG values of the CP exchange points out a higher activation energy as in the corresponding η4-diene metal complexes. 相似文献
Preparation of New Alkylaminofluorosilanes Aminofluorosilanes of the composition RSiF2NR′R″ (R = H, CH3, C2H3, C6H5; R′ = Si(CH3)3; R″ = C(CH3)3; R′ = R″ = i-C3H7), as well as C6H5SiF2N[C(CH3)2CH2]2CH2 are obtained by the reaction of fluorosilanes with the lithium salts of the corresponding amines in a molar ratio 1:1. The further reaction of these compounds with the lithium salts of alkylamines and anilin leads to the formation of the diaminofluorosilanes RSiFNR′R″NHR? (R? = C(CH3)3, i-C3H7, C6H5). The 1H, 19F, 29Si n.m.r. and mass spectra of the above mentioned compounds are reported. 相似文献
Preparation of New Spiro-Alkoxy-Cyclophosphazatrienes New spiro-Alkoxy-cyclophosphazatrienes of the general formula are described. The preparation of the substances and their mass spectroscopic data are reported. 相似文献
New SiMe2R-substituted derivatives of decamethylcyclopentasilane were prepared by different pathways. The halogen compounds where R = F, Cl, Br or I exhibit a strong influence of the substituent on the physical properties of the silicon ring. Hydrolysis of the halides gives a hydroxy compound (R = OH) and takes place extremely slowly, whereas the formation of polysiloxanes is favoured. 相似文献
Zusammenfassung Es wird die Bildung stabiler Sulfoniumylide durch Kondensation verschiedener Sulfoxide mit diversen stark C-H-aciden Verbindungen beschrieben.
The formation of stable sulfonium ylides by condensation of sulfoxides with various strongly C-H-acidic compounds is described.
Compounds of the composition RR′SiFNR″Si(CH3)3 (R = H, F, CH3, C2H5, C3H7, C2H3, C6H5, C(CH3)3; R = F, CH3, C6H5; R″ = CH3, C(CH3)3, Si(CH3)3) are obtained by the reaction of silicontetrafluoride or organo-substituted silicon-fluorides with the lithium salts of alkylsilylamines in a molar ratio of . The disubstituted compounds RSiF(NR′Si(CH3)3)2 (R = H, F, CH3, C2H3, C6H5; R′ = CH3, C(CH3)3) result when the reactants are in a molar-ratio. Likewise the unsymmetrical siliconfluorsilylamines of the formulae F2Si(NRSi(CH3)3) (NR′Si(CH3)3) (R = CH3, R′ = C(CH3)3), as well as the trisubstituted compounds FSi(NCH3Si(CH3)3)3 and FSi(NCH3Si(CH3)3)2(N(Si(CH3)3)2) were made. By reacting phenyltrifluorsilane with dialkylamines () C6H5SiF2NR2(R = CH3, C2H5) was obtained. The IR-, mass-, 1H and 19F NMR spectra of the above-mentioned compounds are reported. 相似文献
