Starting Materials—Chloro Complexes

Binary Compounds. The mthenium fluorides are RuF [51621 -05-7] RuF [71500-16-8] tetrameric (RuF ) [14521 -18-7] (15), and RuF [13693-087-8]. The chlorides of mthenium are RUCI2 [13465-51-5] an insoluble RuCl [10049-08-8] which exists in an a- and p-form, mthenium trichloride ttihydrate [13815-94-6], RuCl3-3H2 0, and RuCl [13465-52-6]. Commercial RuCl3-3H2 0 has a variable composition, consisting of a mixture of chloro, 0x0, hydroxo, and often nitrosyl complexes. The overall mthenium oxidation state is closer to +4 than +3. It is a water-soluble source of mthenium, and is used widely as a starting material. Ruthenium forms bromides, RuBr2 [59201-36-4] and RuBr [14014-88-1], and an iodide, Rul [13896-65-6]. 

The tendency to hydrolyse increases from the chloro to the iodo analogues. Oxohalide technetates are often used as precursors for oxotechnetium complexes, thus making use of their reactivity and good solubility of their tetraalkyl ammonium salts in various organic solvents. Particularly, salts of tetrachloro-oxotechnetate(V) have proven to be such effective starting materials. 

These results were explained by the discovery that the chloro-ruthenium complexes are not the primary photoproducts under CO in 1.0 M CCl /octane solution. Instead Ru(CO>5 proved to be the initial product even after nearly complete photofragmentation of the starting material, and the chlorocarbonyl ruthenium products to be the result of a secondary, dark reaction between the Ru(C0)5 and CCI4 (3) ... 

The elimination reactions of /l-acetoxy sulfones 114 to give the donor-acceptor-substituted allenes 115 by a Julia-Lythgoe process are less conventional (Scheme 7.18) [157]. A new one-step synthesis of allene-l,3-dicarboxylates 118 from acetone derivatives 116 was developed by the use of 2-chloro-l,3-dimethylimidazolinium chloride 117 [158, 159]. This elimination of water follows also the general Scheme 7.17 if a derivative of the enol, resulting from 116, is assumed as an intermediate for an elimination step. More complex processes of starting materials 119 furnished allenyl ketones 120 in high yields [160-162]. 

The chloro complex 68b served as a useful starting material for the preparation of a variety of derivatives containing the [Me2Si(OfBu)(NtBu)]2Y unit [27]. Typical reactions are summarized in Scheme 8. 

The green chloro(nitro) complex [Rh(N0)Cl(N02)(PPh3)2] has often been observed as an intermediate in the preparation of [Rh(NO)Cl2(PPh3)2], but it has only been isolated when [RhCl(PPh3)3] or mms-[RhCl(CO)(PPh3)2] have been used as the starting materials (equations 305-308).244 1318,132S... 

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