Organic chemistry of dinuclear metal centres. Part 1. Combination of alkynes with carbon monoxide at di-iron and diruthenium centres: crystal structure of [Ru₂(CO)(µ-CO){µ-σ:η³-C(O)C₂Ph₂}(η-C₅H₅)₂]

Bond Forming Reactions Involving Isocyanides at Diiron Complexes

“…The reaction requires photolytic activation in order to remove one CO, and the insertion of monosubstituted alkynes into the Fe-C bond is regioselective, with the less hindered alkyne carbon bound to the imine carbon (as shown in Scheme 5). The alkyne insertion described above is consistent with analogous reactions observed in diiron complexes of the type [Fe 2 (Cp) 2 (CO) 3 (L)] in which alkynes insert into the Fe-bridging L ligands (L = CO [67,68], CS [69]). Isocyanide insertion into iron bridging hydride bond is observed in the dinuclear complex [Fe2(μ-H)(μ-PCy2)(CO)4(μ-CO)(dppm)] (8), leading to the formation of the bridging formimidoyl complex 9 (Scheme 4) [61].…”

Additions and intramolecular migrations of nucleophiles in cationic diruthenium μ-allenyl complexes

“…A further strategy for the preparation of l-g 1 :g 2 allenyl complexes was recently reported [10], whereby the diruthenium complexes [Ru 2 (CO)(l-CO){l-g 1 :g 3 -C a (H)C b C c (OH)(Me)(R)-C(O)}(Cp) 2 ] [R = Me, 1a; R = Ph, 1b], prepared from the cyclopentenone adduct [Ru 2 (CO)(l-CO){l-g 1 :g 3 -C(Ph)-C(Ph)C(O)}(Cp) 2 ] by alkyne exchange [11], are treated with HBF 4 , resulting in formation of the allenyl [Ru 2 -(CO) 2 (l-CO){l-g 1 : g 2 -C a (H)@C b @C c (Me)(R)}(Cp) 2 ] [BF 4 ] [R = Me, 2a; R = Ph, 2b] (Scheme 1) [12].…”

A Remarkable Organometallic Transformation on a Cage‐Incarcerated Dinuclear Ruthenium Complex

“…To our surprise, alkyne complex 4 a was not the final product in this reaction, but a reaction intermediate trapped by cage 1 . When extracted from the cage with CH 2 Cl 2 , 4 a immediately rearranged into diruthenacyclopentenone 5 a by intramolecular CO insertion 13. The rearranged product 5 a was isolated by column chromatography on alumina and fully characterized by NMR and IR spectroscopy.…”

“…The rearranged structure of 5 a was confirmed by X‐ray crystallographic analysis (Figure 3 a). The Ru1 atom was intramolecularly η 2 ‐coordinated by the olefin moiety while the Ru2 atom was σ‐coordinated by the olefinic carbon atom (C5) 13. The C4C5 bond was considerably longer (1.4240(19) Å) than the average CC bond (1.33 Å) because of the backdonation from the two metal centers through η 2 and σ coordination.…”