Reactions of diacetylene ligands with trinuclear clusters II. Reactions of hexa-2,4-diyne-1,6-diol and 1,4-diphenyl-1,3-butadiyne with Ru3(CO)12

Ferrole-type compounds containing thiophenic or thiepinic rings in the 3,4-positions of the metallacycle

“…Similar rupture of a S-C bond and coupling between C"CR groups have been described in the reaction of the alkylalkynyl thioethers EtSC"CR (R = Me, Ph) with Fe 3 (CO) 12 in refluxing hexane, although the trinuclear clusters [Fe 3 (CO)8 {l 3 -(SEt)C@C(R)C(R)@C)}(l-SEt)] and [Fe 3 (CO) 8 {l 3 -(R)C@C(SEt)C(R)@C)}(l-SEt)] (R = Me or Ph)[14] which contain a bridging thiolate ligand and a ferrole unit in the molecule have been obtained instead of dinuclear species.In contrast, compound Ru 2 (CO)6 [l-g 2 ,g 4 -(Me 3 Si)C@C(SC" CFc)C(H)@C(Fc)] 4 is formed by a C-C coupling reaction between one of the C"C triple bond in the thioether FcC"CSC"…”

“…and a molecule of the alkyne HC"CFc. In this case, cleavage of the S-C bond does not occur and, as we mentioned before, examples are reported of diynes or poly-ynes which use only one of the C"C triple bond to yield ferrole-type derivatives [8][9][10][11].…”

“…Metal carbonyls of the iron triad react with alkynes to afford ''ferrole-type" species such as Fe 2 (CO) 6 -[(CH 3 OCH 2 )C@ C(H)C(H)@C(CH 2 OCH 3 )] [1], Fe 2 (CO) 6 [(R)C@C(H)-C(H)@C(R)] (R = 17a-estradiol) [2], (R = Fc) [3], Fe 2 (CO) 6 [(CH 3 COO)C@C(Ph)C(Ph)@ C(OOCCH 3 )] [4], Fe 2 (CO) 6 [C 4 (SMe) 4 ] [5], Ru 2 (CO) 6 [{CH 3 (H 2 C@)} C@C(Et)C{(@CH 2 )CH 3 )}@C(Et)] [6], [Os 2 (CO) 6 -(C 4 H 4 )] [7]. Also, the diynes RC"C-C"R (R = Ph, Fc) and the poly-yne Me 3 SiC"C-C"C-C"CSiMe 3 use only one of their carbon-carbon triple bonds to give the complexes Ru 2 CO 6 [l-g 2 ,g 4 -(Ph)C@C(C"CPh)C(PhC "C)@C(Ph)] [8], Os 2 CO 6 [l-g 2 ,g 4 -(FcC"C)-C@C(Fc)C(Fc)@C(C" CFc)] [9], Ru 2 CO 6 [l-g 2 ,g 4 -(Me 3 SiC"C)C@C-(C"CSiMe 3 )C(C" CSiMe 3 )@C(C"CSiMe 3 )] [10] and Ru 2 (CO) 6 -[C 4 Fc 2 (C"CFc) 2 ] [11]. Some ferrole-type compounds have been reported to act as intermediates in synthesis of organic products [4,12].…”

Crystal structure of [μ-1κ2 C 1,C 4:2(1,2,3,4-η)-1,2,3,4-tetraphenylbuta-1,3-diene-1,4-diyl]bis(tricarbonylosmium)(Os—Os)

“…one in which the carbonyl ligands of the M 2 (CO) 6 units are eclipsed in a so-called sawhorse conformation, or one in which the carbonyls are staggered with one CO semibridging the metal-metal bond. Ferroles (M = Fe) almost always adopt the staggered non-sawhorse conformation (Kumar et al, 2014;Iyoda et al, 1997;Jeannin et al, 1994;Heim et al, 1992;Daran & Jeannin, 1984), while ruthenoles (M = Ru) display an equal propensity to adopt either the sawhorse or the nonsawhorse conformation (Yang, 2014;Mathur et al, 2008Mathur et al, , 2014Tunik et al, 1997). Only two osmole (M = Os) complexes have been examined by X-ray crystallographic analysis, and both of them exhibit the sawhorse conformation.…”

Preparation of Mo, Co and iron group heterometallic clusters linked by cyclotetradeca-1,8-diyne ligand

“…It is of interest that Ru 3 (CO) 10 (NCMe) 2 reacts with 1 at 25°C to produce the alkyne-allenyl complex [Cp 2 Mo 2 (CO) 4 ](m,m 3 -h 2 ,h 3 , analogous to 4, is initially afforded, which then undergoes a facile b-C H activation of the alkyne ligand and a CO loss to give 3-allenyl. Tunik and co-workers [16] previously reported the reaction of Ru 3 (CO) 12 and hexa-2,4diyne-1,6-diol to lead to the alkyne complex Ru 3 (CO) 10 (m 3 -h 2 -HOCH 2 C 2 C 2 CH 2 OH) in 14%, while the transformation from a coordinated alkyne to a hydrido-allenyl moiety has been established in some triosmium systems [6,[17][18][19]. Thermolysis of 3-allenyl at 70°C results in a hydrogen migration to afford 3-allyl.…”