Reactions of Ru3(CO)12 with asymmetrically substituted acetylenes. A new type of interaction between acetylenes and a metal-atom cluster

Ligand‐Controlled Regio‐ and Stereoselective Addition of Carboxylic Acids Onto Terminal Alkynes Catalyzed by Carbonylruthenium(0) Complexes

“…The studied catalysts were classified into three groups: (i) trinuclear clusters: Ru 3 (CO) 12 (1) and Ru 3 (CO) 9 -(PPh 3 ) 3 (2); (ii) mononuclear diene complexes: Ru(CO) 3 -(1,3-cyclohexadiene)(3),Ru(CO) 3 (α-terpinene)(4),Ru(CO) 3 -(2,5-norbornadiene) (5); and (iii) mononuclear phosphane complexes: Ru(CO) 3 [P(OEt 3 ) 3 ] 2 (6), Ru(CO) 4 (PPh 3 ) (7), Ru(CO) 3 (PPh 3 ) 2 (8) and Ru(CO) 3 (PCy 3 ) 2 (9). The syntheses of 2-9 from commercially available 1 were straightforward.…”

“…Only one, or some, of these species may exhibit catalytic behavior. [12,13] Hence the slightly lower yield can be attributed to the extra induction time required for conversion to occur, together with a lower catalytic loading due to formation of inactive species. The regioselectivity of the system was not affected by the substituent on the acid, as inferred from the ratio of antiMarkovnikov to total enol ester yields (Table 1).…”

“…Triruthenium Dodecacarbonyl, Ru 3 (CO) 12 (1) (Aldrich, 99 %) was recrystallized from cyclohexane before use. Phenylacetylene, 1-heptyne, glacial acetic acid, pivalic acid, benzoic acid, 1,3-cyclohexadiene, 2,5-norbornadiene, α-terpinene, triphenylphosphane, tricyclohexylphosphane and triethylphosphite were obtained from Aldrich and used without further purification.…”

The Hydrido‐Transition Metal Cluster Complexes

“…A variety of 1 ,2-di-uqz -ole fin complexes of structure type X have been isolated in the reaction of a variety of linear or cyclic olefins with R u~( C O )~ 2(87), or H4Ru4(CO)1 2(28, 29) (see listings under H2M3C2, Section V). Under more vigorous conditions, further interactions with the hydrocarbon are possible, leading to HM3C3 type complexes, shown in Scheme 4 (2,22,33,62,102,119,121,122,137,213,239). As indicated for the Os3 cluster above (73), the l-u-bis-~2-aUenyl complex XII is the kinetically favored product; however, thermal treatment leads to the thermodynamically stable 1 ,3-di-uq3 -ally1 complex (XIII).…”

Carbon–carbon coupling on tetrahedral iridium clusters: X-ray molecular structures and multinuclear NMR studies of the two isomeric forms of [Ir4(CO)6(μ3-η2-HCCPh)(μ2-η4-C4H2Ph2)(μ-PPh2)2]

“…Systematic studies involving the modes of interaction of alkynes [1][2][3][4][5][6], activation of C-C [7,8] and C-H [9,10] bonds, cyclotrimerization [10], oligomerization [11][12][13][14] and coupling with other ligands such as acetylides and phosphinoalkynes [15][16][17], incorporation of CO [16] and insertion into M-P bonds [18,19] have been performed and several reaction pathways elucidated, especially those involving clusters of the iron triad [2,20,21]. In contrast, reports on the reactions of iridium clusters with alkynes are rare, most probably due to the lack of suitably reactive starting materials besides [Ir 4 (CO) 12 ] and [Ir 6 (CO) 16 ].…”