Activation of methanol in the reaction of [Fe3(CO)12] with 1-phenylprop-2-yn-1-ol; crystal structures of and chemical relationships between [Fe3(CO)9(μ-CO){(CC C(H)Ph}] and [Fe2(CO)6{Ph(H)CCCHC(OMe)O}]

Reactions of Fe3(CO)12 with 2-methyl-3-butyn-1-ol and 3-pentyn-1-ol under basic methanolic conditions: The crystal structures of Fe2(CO)6(μ-CO)(μ-η2-[HCC{C(CH3)2}C(O)(OCH3)]) and of (μ-H)Fe3(CO)9(μ3-η3-[H3CCC(CH2)(CH2)CO])

“…The reaction of mbo with Fe 3 (CO) 12 in hydrocarbons has been already reported [6]. Main products were the allenylidenic derivative Fe 3 (CO) 9 (l-CO)(C@C@CMe 2 ) (complex a), the open cluster Fe 3 (CO) 6 (l-CO) 2 [HC 2 {CMe 2 (OH)}{HC 2 C(@CH 2 )Me}] and the ferrole Fe 2 (CO) 6 [HC 2 {CMe 2 (OH)}{HC 2 C(@CH 2 )Me}] (complex 2 in this work) in one isomer each.…”

“…plates as described above. The yields of the products (either under basic methanolic and under thermal conditions) are given on the Fe 3 (CO) 12 consumed.…”

“…6 mmol) of Fe 3 (CO) 12 were suspended in heptane under N 2 and 1.5 cm 3 (ca. 18 mmol) of pol were added.…”

“…Two main dehydration pathways have been found, that is: (a) release of the terminal alkynic hydrogen and of the OH group to give the allenilydene clusters M 3 (CO) 9 (l-CO)(l 3 -g 2 -C@C@CRR 0 ) and (b) loss of the OH and of the hydrogen of an alkynic substituent to give vinyl-acetylide substituted clusters [4]. Also different products are formed when the same alkyne is reacted with Fe 3 (CO) 12 under thermal or under basic methanolic conditions (CH 3 OH/KOH solution, followed by acidification) [3d,3e]; this was expected considering that, in these conditions, the anion [HFe 3 (CO) 11 ] À is formed. Finally, the nature of the alkyne (e.g.…”

“…On these grounds, a systematic study of the reactivity of different alkynols with the M 3 (CO) 12 (M = Fe, Ru) carbonyls was undertook. As a part of this study the behaviour of two isomeric alkynes towards Fe 3 (CO) 12 is compared: the terminal 2-methyl-3-butyn-2-ol [HC"CC(Me) 2 OH, mbo] and the internal 3-pentyn-1-ol [EtC"CCH 2 OH, pol] have been reacted with the iron carbonyl in CH 3 OH/KOH solution (followed by acidification with HCl). With mbo the main reaction product is Fe 2 (CO) 6 (l-CO)(l-g 2 -[HCC{@C(CH 3 ) 2 } C(@O)OCH 3 ]) (complex 1) containing an acetate ligand formed by coupling of an allenilydene with a coordinated CO and a methoxy group.…”