Reactions of ruthenium carbonyl clusters with alkynes

Photochemical reactions of Fe(CO)5 with FcCCH in the presence of S-powder and CS2: Synthesis and characterization of [{μ-SC(H)C(Fc)S}(CO)6Fe2], [μ-SC(O)C(H)C(Fc)S}(CO)6Fe2]; cis-[μ-η1:η2:η1:η1-{C(Fc)C(H)CS2C(H)C(Fc)}(CO)6Fe2] and trans -[μ-η1:η2:η1:η1-{C(Fc)C(H)CS2C(Fc)C(H)}(CO)6Fe2]

“…The IR spectra of 1 and 2 display carbonyl stretching patterns typically observed in the spectra of compounds containing the Fe 2 (CO) 6 groups. The spectrum of compound 1 displays a carbonyl stretching pattern which is identical to that observed for earlier reported [{l-EC(H)@C(R)E 0 }-(CO) 6 Fe 2 ] (E, E 0 = S, Se,Te; R = Ph, Th, C"CCH 3 ) [9][10][11][12][13][14][15][16][17]. Compound 2 shows a band due to the presence of a ketonic carbonyl group at 1655 cm À1 , in addition to the terminal carbonyl bands.…”

“…1 and 2, respectively. Acetylenes (RC"CH, R = H, Ph) are known to add across the chalcogen-chalcogen bonds of [Fe 2 (CO) 6 -(l-EE 0 )] (for all combinations of E, E 0 = S, Se, Te except E = E 0 = S) to yield the adducts [Fe 2 (CO) 6 {l-EC(R)@ C(H)E 0 }]. The S 2 analog, [Fe 2 (CO) 6 {l-SC(H)@C(H)S}] has been obtained by reacting HC"CMgBr with [Fe 2 -(CO) 6 S 2 ], followed by protonation with CF 3 CO 2 H; and its identification is based on spectrometric characterisation.…”

“…Acetylenes (RC"CH, R = H, Ph) are known to add across the chalcogen-chalcogen bonds of [Fe 2 (CO) 6 -(l-EE 0 )] (for all combinations of E, E 0 = S, Se, Te except E = E 0 = S) to yield the adducts [Fe 2 (CO) 6 {l-EC(R)@ C(H)E 0 }]. The S 2 analog, [Fe 2 (CO) 6 {l-SC(H)@C(H)S}] has been obtained by reacting HC"CMgBr with [Fe 2 -(CO) 6 S 2 ], followed by protonation with CF 3 CO 2 H; and its identification is based on spectrometric characterisation. We attempted to prepare 1 by the method used for obtaining [Fe 2 (CO) 6 {l-EC(R)@C(H)E 0 }], of room temperature stirring of solution containing [Fe 2 (CO) 6 S 2 ] with ferrocenylacetylene in presence of sodium acetate, but did not observe any formation of 1.…”

“…Photolysis of solution containing Fe(CO) 5 , ferrocenylacetylene and S-powder When a mixture of Fe(CO) 5 , ferrocenylacetylene and S-powder in hexane solvent was photolysed under constant bubbling of argon for 10 min at À30°C, formation of new adducts [{l-SC(H)@C(Fc)S}(CO) 6 Fe 2 ] (1) and [l-SC(O)-C(H)@C(Fc)S}(CO) 6 Fe 2 ] (2) was observed (Scheme 1). These were isolated by chromatographic work-up as airstable crystalline solids.…”

“…With less bulky acetylenes, formation of substituted quinones was not observed. Contrast in behavior of ferrocenylacetylene and phenylacetylene has also been observed in their reactions with mixtures of [Fe 3 (CO) 9 were treated with [Fe 3 (CO) 9 (l 3 -S) 2 ] in the presence of different acetylenes HC"CR (R = Ph), n-Bu or Fc{(g 5 -C 5 H 5 )(g 5 -C 5 H 4 )Fe}, we isolated mixed-metal clusters [Fe 3 M[(g 5 -C 5 Me 5 )(CO) 6 [8].…”