Reaction of Fe3(CO)12 with but-2-yn-1,4-diol, 1,4-dichloro-but-2-yne, propargyl-alcohol and propargyl-chloride.

Reactions of Co2(CO)8 and of Co2(CO)6L (L=3-pentyn-1-ol, 1,4-butyn-diol or 2-methyl-3-butyn-2-ol) with 2(diphenylphosphino)ethyl-trietoxysilane and tris(hydroxymethyl)phosphine for applications to new sol–gel materials

“…Some silica-based inorganic-organometallic materials are also known; for example metal carbonyl clusters substituted with alkynic ligands containing OH functionalities or Si(OCH 2 CH 3 ) 3 groups can be grafted to silica-based inorganic materials [3]. These syntheses are however made difficult because of exchange reactions between the coordinated alkynols and the sol-gel materials and mostly because several alkynols undergo loss of their functionalities when reacted with iron [4] or ruthenium [5] carbonyls.…”

“…These syntheses are however made difficult because of exchange reactions between the coordinated alkynols and the sol-gel materials and mostly because several alkynols undergo loss of their functionalities when reacted with iron [4] or ruthenium [5] carbonyls. We have therefore attempted the synthesis of new ligands by reacting the alkynols with triethoxysilyl-propyl-isocyanate (tsi) [(H 3 CCH 2 O) 3 Si(CH 2 ) 3 NCO] [6] and other alkoxysilyl-contaning ligands [7].…”

Synthesis of Enantiopure Ruthenium Tricarbonyl Complexes of a Bicyclic Cyclopentadienone Derivative

“…[6] In this homocoupling reaction, two alkynes react with Fe(CO) 5 under a CO atmosphere to give the symmetrically substituted cyclopentadienone-Fe(CO) 3 complexes. [7] Herein is reported a general approach to cyclopentadienone-ruthenium carbonyl complexes of chiral cyclopentadienone derivatives, which may be useful in asymmetric synthesis, by cross-coupling of tethered diynes by Ru 3 (CO) 12 -promoted cyclocarbonylation (Scheme 1). [8] Scheme 1.…”

“…30 and 24 % yields, respectively (Scheme 4). The reaction of dimethyl malonate 11 with Ru 3 (CO) 12 provided two ruthenium-containing compounds: the usual cyclopentadienone adduct 14 [R f = 0.33 (10 % EtOAc/nhexane); 36 % yield after column chromatography and recrystallization] as colorless crystals and a slightly lesspolar material [R f = 0.41 (10 % EtOAc/n-hexane)] as yellowish crystals, which exhibited almost the same NMR spectra but later was shown to be ruthenacylopentadiene [12] 15 (18 % yield after column chromatography and recrystallization) by X-ray crystallography (Scheme 5). However, the more reactive tris(acetonitrile) complex Ru 3 (CO) 9 -(MeCN) 3 [13] did not give a significant increase in yield of cyclopentadienone adduct 14 (ca.…”

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 of the reactions with TSPA was the allylic complex (l-H)Ru 3 (CO) 9 (l 3 -g 3 -C 3 H 3 ) (complex 1) [1] whereas from the reactions of BUD we obtained the butadienylic open cluster (l-Cl)Ru 3 (CO) 9 [l 3 -g 4 -H 2 CCC(H)CH 2 ] (complex 2) [2]; finally, when Ru 3 (CO) 12 was reacted with DCB, the complex (l-H) 2 Ru 3 (CO) 9 [H 2 C@C(H)C"CC(@O)OCH 3 ] (3) [3] containing a ene-yne bound in parallel fashion [4] was obtained. The structures found for complexes 1-3 are shown in Scheme 2.…”