Ruthenium complexes, reactions neutral species

Although this spectrum does not correspond to any particular ruthenium carbonyl complex, it is consistent with the presence of one or more anionic ruthenium carbonyl complexes, perhaps along with neutral species. Work is in progress with a variable path-length, high pressure infrared cell designed by Prof. A. King, to provide better characterization of species actually present under reaction conditions. 

Two distinct classes of promoters have been identified for the reaction simple iodide complexes of zinc, cadmium, mercury, indium and gallium, and carbonyl complexes of tungsten, rhenium, ruthenium and osmium. The promoters exhibit a unique synergy with iodide salts, such as hthium iodide, under low water conditions. Both main group and transition metal salts can influence the equilibria of the iodide species involved. A rate maximum exists under low water conditions and optimization of the process parameters gives acetic acid with a selectivity in excess of 99% based upon methanol. IR spectroscopic studies have shown that the salts abstract iodide from the ionic methyl iridium species and that in the resulting neutral species the migration is 800 times faster [127]. 

Reactions between salts of [m Jo-7-CBioHi3] and [Fc3(CO)i2] afford the mononuclear anionic iron compound [2,2,2-(CO)3-c/o5o-2,l-FeCBioHn], typically isolated as its [N(PPh3)2] salt (11) (Chart 4). No anionic triiron complex analogous to 5 and 7 is formed in this reaction. The anionic mononuclear iron, ruthenium and osmium complexes and the previously mentioned neutral mononuclear ruthenium dicarbollide complex 4, obtained from [Ru3(CO)i2] and /Jo-7,8-C2BgHi3, are iso-lobal with the cyclopentadienide species [Mn(CO)3(ri-C5H5)] and [Fe(CO)3 (il-CsHs)]. ... 

Ruthenium vinylidene species can be transformed into small carbocyclic rings via carbocyclization reactions. Ruthenium vinylidene complex 2, generated from the electrophilic reaction of alkyne complex 1 with haloalkanes, was deprotonated with "BU4NOH to give the unprecedented neutral cyclopropenyl complex 3 (Scheme 6.2) [5]. Gimeno and Bassetti prepared ruthenium vinylidene species 4a and 4b bearing a pendent vinyl group when these complexes were heated in chloroform for a brief period, cyclobutylidene products 5a and Sb formed via a [2 + 2] cycloaddition between the vinylidene Ca=Cp bond and olefin (Scheme 6.3) [6]. 

It is noteworthy that the addition of thiols to form propargylic sulfides is not catalysed by the neutral complex [Cp RuCl(p2-SR)2RuCl(Cp )], but requires the utilization of a cationic precursor such as [Cp RuCl(p2-SMe)2Ru(Cp )(H20)]0Tf [85]. With this catalytic system,propargylic alcohols bearing an internal triple bond are also transformed into propargylic sulfides, which indicates that in this special case, the reaction does not involve a ruthenium allenylidene as an active species. 

Most efforts to explore the reactivity of ruthenium carbene complexes have employed the alkoxycarbene species so readily synthesized from the inter- or intramolecular reaction of vinylidene complexes with alcohols. These electrophilic alkoxycarbene complexes exhibit only limited reactivity at Ca, primarily with hydride reagents. For example, treatment of the 2-oxacyclopentylidene complex 97 with NaAlH2(OCH2CH2OMe)2 affords the neutral 2-tetrahydrofuranyl complex (98) [Eq. (89)] (55), as was anticipated from similar reductions of iron carbene complexes (87). 

---