Ruthenium adduct formation with

Iron(in) chloride is a common impurity in commercial phosgene at the 0.08-0.2% level [1168]. Attempts to isolate an adduct between phosgene and iron(Ill) chloride were unsuccessful [1012], and a tensimetric titration of ruthenium(IIl) chloride with phosgene showed no evidence for complex formation [ICIl]. 

For coordinating and sensing luminescent lanthanide ions, a luminescent ruthenium bipyridyl complex has been covalently linked to one, two or six lower rim acid-amide modified caUx[4]arene moieties in receptors 155-157. All these complexes coordinated with lanthanide ions, Nd , Eu and Tb, with the formation of adducts of variable stoichiometries. The adduct formation affected the Ru luminescence, which was strongly quenched by Nd ion, increased by the Tb ion and moderately quenched or increased by Eu ion (2004IC3965). 

Ando. I. Ishimura. D. Ujimoto. K. Kurihara. H. Effect of second-sphere coordination 3. Adduct formation of mononuclear and binuclear ruthenium-ammine complexes with 18-crown-6 ether. Inorg. Chem. 1994. 33, 5010-5014. 

Directed ruthenium-catalyzed hydroesterifications of alkenes, employing 2-pyridylmethyl formate, leads to esters (Equation (136)). With vinyl ethers a-adducts are obtained (Equation (137)). 

Itoh and coworkers111 carried out tandem [2 + 2 + 2]/[4 + 2] cycloadditions catalyzed by a ruthenium catalyst. The reaction of diyne 147 with excess norbomene 148 in the presence of ruthenium catalyst 153, for example, afforded 149. Adduct 150 either dissociated from the catalyst or reacted with another equivalent of norbornene. In the latter case, a ruthenium catalyzed Diels-Alder reaction occurred, affording hexacyclic adduct 152 via 151 (equation 43). Compounds 150 and 152 were obtained in yields of 78% and 10%, respectively. Both cycloaddition reactions proceeded with complete stereoselectivity. When 1,6-heptadiyne was used instead of 147, only trace amounts of a cycloadduct were obtained. Replacing norbornene by norbornadiene, which was expected to result in polymer formation, did not afford any adduct at all. 

Formation of the adduct chlorine trifluoride—ruthenium pentafluoride by reaction with ruthenium metal at ambient temperature is extremely violent. 

SiMe3, x = 1-2 R = Me, x = 1-3), have also been prepared from the reaction of HCl(g) with the alkyl complexes (286). Reaction with Au(PPh3)Cl results in the formation of [Ru(N)ClMe3] and Au(PPh3)Me from [Ru(N)Me4], in a manner analogous to that of the HC1 reaction (286). In contrast to the related osmium complexes, Lewis acid adducts of the ruthenium nitrides are thermally unstable. 

The formation of vinylcarbamates is restricted to terminal alkynes, which is in line with the formation of a metal vinylidene intermediate, and also to secondary amines. Indeed, a catalytic reaction also takes place under similar conditions with primary aliphatic amines but it leads to the formation of symmetrical ureas (Scheme 3) [10]. The catalytic system generated in this case is also thought to proceed via a ruthenium vinylidene active species and is very efficient for the formal elimination of water by formation of an organic adduct. The proposed general catalytic cycle, which applies for the formation of vinylcarbamates and ureas, is shown in Scheme 4 [11]. 

Pericyclic reactions involving thiophenes have been utilized to prepare a variety of complex heterocycles. The intramolecular Diels-Alder reaction of 2-vinylbenzo[i]thiophene 92 produced a pair of tetracyclic adducts 93 and 94 <02TL3963>. Coupling of Fischer carbene 96 with 3-alkynylthiophene 95 led to the formation of thieno[2,3-c]pyran-3-one 97 in one step <02JOC4177>. An intramolecular cycloaddition of 97 then afforded tetracyclic adduct 98. A ruthenium-catalyzed cyclodimerization reaction involving bis-thienyl acetylene derivatives was... 

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