Formation of novel conjugated polycarbon–metal systems via metal migration on a M–CC–CC–M linkage

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]

“…Under photolytic conditions, it is possible that a partial decomposition of Fe(CO) 5 to form Fe(CO) x fragments influences the reactivity of ferrocenylacetylene towards the synthesis. Structures of 1 and 2 both feature a butterfly Fe 2 (CO) 6 Formation of 2, which can formally be regarded as a CO insertion product of 1, was not observed when a solution of 1 was bubbled with CO (Scheme 2) under thermolytic or photolytic conditions.…”

“…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.…”

“…Indeed, the C(olefin)-Fe distances in 5 and 6 (average C(17)-Fe (2) [21] and in [Fe(CO) 3 (g 2 C 6 H 4 (CH@ CH 2 )(PPh 2 ))] (2.05 Å ) [22]. However, the C(Fc)@CCS 2 bond distances of 1.418(9) Å in 5 and 1.412(7) Å in 6 are somewhat longer than the C@C bond distance of 1.35-1.39 Å in [Fe(g 5 C 5 H 4 E I CH 2 C"CH)g 5 is similar to the S-C-S bond angle of 110.6(2)°in [(g 5 -C 5 H 5 )Mo(CO) 2 (g 2 -S 2 CC"CPh)], and 108.6(6)°in [(g 5 -C 5 Me 5 )Mo(CO) 2 CS 2 ){W(CO) 5 } 2 C"CPh] [18].…”

“…Fe(CO) 5 (1), and a yellow FcC CH. Further elution with acetone/hexane (2:98 v/v) mixture yielded a red band of trans-[l-g 1 :g 2 :g 1 :g 1 -{C(Fc)@ C(H)CS 2 C(H)@C(Fc)}(CO) 6 Fe 2 ] (6); and a red cis-[lg 1 :g 2 :g 1 :g 1 -{C(Fc)@C(H)CS 2 C(Fc)@C(H)}(CO) 6 Fe 2 ] (5).…”

Electronic Structure and Chain‐Length Effects in Diplatinum Polyynediyl Complexes trans,trans‐[(X)(R3P)2Pt(CC)nPt(PR3)2(X)]: A Computational Investigation

“…[7,8,[10][11][12][13][14] This paper has attempted to anticipate future developments by providing a comprehensive structural and electronic grammar for complexes with polyynediyl or (CC) n linkages of medium to long to infinite lengths. The computational results nicely rationalize the somewhat scant existing data, including phenomena that are at first glance surprising.…”