A general class of stable alkyl halide complexes: synthesis, structure, and reactivity of alkyl iodide complexes of the formula [(.eta.5-C5H5)Re(NO)(PPh3)(IR)]+ BF4-

1987 ◽  
Vol 109 (24) ◽  
pp. 7560-7561 ◽  
Author(s):  
Charles H. Winter ◽  
Atta M. Arif ◽  
J. A. Gladysz
Keyword(s):  
General Class ◽  
Alkyl Halide ◽  
Alkyl Iodide ◽  
Halide Complexes

Some Metal Halide – Phosphorus Halide – Alkyl Halide Complexes. Part III. The µ-Trihalohexahalodimetallate Ions of Titanium and Zirconium

1974 ◽  
Vol 52 (16) ◽  
pp. 2880-2888 ◽  
Author(s):  
Joseph I. Bullock ◽  
Frederick W. Parrett ◽  
Nicholas J. Taylor
Keyword(s):  
Vibrational Spectroscopy ◽  
Titanium Tetrachloride ◽  
Alkyl Halide ◽  
Metal Halide ◽  
The Other ◽  
Butyl Chloride ◽  
Halide Complexes ◽  
Titanium Tetrabromide

Titanium tetrachloride reacts rapidly with trichloro-, tribromo- and methyldichlorophosphine in the presence of t-butyl chloride to give compounds containing a phosphonium cation R1R2PX2+ (R1 = t-butyl, R2 = chloride, bromide, or methyl, X = chloride or bromide) and the principal metal-containing anion, Ti2Cl9−. For tribromophosphine and t-butyl chloride a stoichiometric product, [ButPBr3][Ti2Cl9] was obtained which was characterized using vibrational spectroscopy. The other reactions gave non-stoichiometric materials, the sublimates of which may contain higher polymeric anions whilst the residues contained TiCl5− along with the parent dimeric anion.Zirconium tetrachloride and titanium tetrabromide reacted in a similar way to give the new ions Zr2Cl9− and Ti2Br9− in stoichiometric reactions.

Primary and secondary 5-(alkyloxy)thianthrenium perchlorates. Characterization with 1H NMR spectroscopy, reactions with iodide and bromide ion, and thermal decomposition in solution

1998 ◽  
Vol 76 (6) ◽  
pp. 695-702 ◽  
Author(s):  
Wenyi Zhao ◽  
Henry J Shine
Keyword(s):  
Nmr Spectroscopy ◽  
Alkyl Group ◽  
Alkyl Halide ◽  
Cation Radical ◽  
Side Reaction ◽  
Alkyl Iodide ◽  
Order Kinetic ◽  
H Nmr ◽  
Bromide Ion ◽  
Stereogenic Center

A series of 5-(alkyloxy)thianthrenium perchlorates has been made in which the alkyl group is primary (1a-1p) and secondary (2a-2g). Preparations were carried out by reaction of the corresponding alkanol with thianthrene cation radical perchlorate in CH2Cl2 solution followed by precipitation of the perchlorate salt with dry ether. 1H NMR spectroscopy reveals that the presence of a stereogenic center in the alkyl group causes inequivalence in the ordinarily paired protons (e.g., H-4, H-6) of the thianthrenium ring. Reaction of iodide and bromide ion with primary alkyl-group compounds (e.g., methyl, ethyl, propyl, butyl) gave the alkyl halide in very good yield and by a second-order kinetic displacement. The second product was thianthrene 5-oxide (ThO). Rate constants for some of these reactions are reported. Reaction of secondary alkyl group compounds (e.g., 2-propyl, 2-pentyl, 2-hexyl, and 3-hexyl) with iodide ion gave good yields of alkyl iodide but also increasing evidence for a side reaction at the sulfonium sulfur, leading to I2, thianthrene, and secondary alkanol. Decomposition of some compounds at 100°C in solution (acetonitrile or 1,2-dichloroethane) was studied and gave alkene(s) and ThO.Key words: thianthrene cation radical, 5-(alkyloxy)thianthrenium perchlorates.

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