Complexes of transition metal carbonyls with alkynes. Closo- and nido-pentagonal bipyramidal clusters

The reaction of Ru3(CO)12 with 1,4-dichloro-but-2-yne in basic methanolic solution. Synthesis and crystal structure of (μ-H)2Ru3(CO)9{μ3-η2-[H2CC(H)CCC(O)OCH3]}

“…Somewhat related to this behaviour is the recently reported synthesis of Ru 3 (CO) 12 from [Ru(CO) 2 Cl 2 ] n in a reaction involving KOH and 2-ethoxyethanol, formation of formyl groups (WGSR reaction) and loss of chlorine [6]. In contrast, uptake of HCl in the reaction of Ru 3 (CO) 12 with BUD in conditions comparable with those used in this work leads to the open cluster (l-Cl)Ru 3 -(CO) 9 [H 2 CCC(H)CH 2 ] (2c) [1b] discussed below.…”

“…One is represented by the thermal reactions of Ru 3 (CO) 12 with t-butyl-acetylene or with alkynols to form oxygenated heterocycles still coordinated to the cluster in a fully elucidated reaction sequence [8]. Addition of a phosphine at the ferrole-like derivative [9] Fe 2 (CO) 6 (C 2 Et 2 ) 2 results in the insertion of CO and formation of a ketonic flyover complex, a precursor of the formation of a tropone [10]. Finally, insertion of a CO during the oligomerization of isopropenylacetylene on Fe 3 (CO) 12 has been reported [11]; open cluster isomers were obtained.…”

“…Loss of substituents has already been observed for trimethylsilyl-propargyl alcohol (TSPA) and diethylamino-1-propyne [1]; the main product of the reactions of these ligands with Ru 3 (CO) 12 under basic methanolic solution was the hydridic allyl complex (l-H)Ru 3 -(CO) 9 [l 3 -g 3 -(HCCHCH)] (2b). In contrast, the reaction of the ruthenium carbonyl with BUD in the same conditions, lead to the chlorine-bridged (l-Cl)Ru 3 (CO) 9 [l 3 -g 4 -(H 2 CCCHCH 2 )] (2c), an open cluster presumably obtained upon addition of HCl [1b].…”

“…In contrast, the reaction of the ruthenium carbonyl with BUD in the same conditions, lead to the chlorine-bridged (l-Cl)Ru 3 (CO) 9 [l 3 -g 4 -(H 2 CCCHCH 2 )] (2c), an open cluster presumably obtained upon addition of HCl [1b]. Complex 2c contains a C 4 H 5 ligand ''isomeric'' with that found in 2.…”

Reactions of Ru3(CO)12 with 2-pentynal-diethyl-acetal. The crystal structure of Ru2(CO)6[μ-η4-{EtC2C(H)(OEt)2}CO{EtC2C(H)(OEt)2}] and its reactivity towards tetraethyl-orthosilicate

“…The main product obtained, in high yields, is the title complex (4) Ru 2 -(CO) 6 [l-g 4 -{EtC 2 C(H)(OEt) 2 }CO{EtC 2 C(H)(OEt) 2 }]; a minor complex (5) has been identified as the ferrolelike Ru 2 (CO) 6 (PDA) 2 .…”