Reaction of [Os3H2(CO)10] with the diyne Me3SiC2C2SiMe3 and the reactivity of the products towards [Co2(CO)8]: the X-ray structures of [Os3(μ-H)(CO)10{μ-η1-η2-HC2(SiMe3)C2(SiMe3)}], [Os3(μ-CO)(CO)9{μ3-η2-Me3SiC2C2SiMe3}] and [Os3(μ-H)(CO)9{μ3-η1:η2-;μ-η2-Me3SiC2C2[Co2(CO)6]}]

Coordination Behavior and Transformations of Thienyl-Substituted Diacetylenes upon Coordination to Os3H2(CO)10

“…The cluster [Os 3 H(CO) 10 (η 1 :η 1 -OC 4 H 2 CCH 3 )] has been shown to undergo an aldol condensation reaction with aromatic aldehydes . Similar cyclization products have also been observed in the reaction of Os 3 H 2 (CO) 10 with other substituted diynes RCC–CCR′ (R = Ph, R′ = CH 2 NHPh; R = Ph, R′ = CH 2 NHCH 2 Ph; R = R′ = CH 2 NHPh; R = R′ = C 5 H 4 N). , Reactions involving Os 3 H 2 (CO) 10 and Me 3 SiCC–CCSiMe 3 do not result in cyclization products due to the 1,2-shift of the SiMe 3 stabilizing the ethynyl ligand . Similarly, a 1,2-shift of one of the ferrocenyl groups along the butadiyne chain has been suggested to account for the products of the reaction of FcCC–CCFc with [Os 3 (μ-H)(CO) 10 (μ-η 2 -NC 5 H 4 )]…”

“…4b,7 Reactions involving Os 3 H 2 -(CO) 10 and Me 3 SiCtCÀCtCSiMe 3 do not result in cyclization products due to the 1,2-shift of the SiMe 3 stabilizing the ethynyl ligand. 8 Similarly, a 1,2-shift of one of the ferrocenyl groups along the butadiyne chain has been suggested to account for the products of the reaction of FcCtCÀCtCFc with [Os 3 (μ-H)(CO) 10 (μ-η 2 -NC 5 H 4 )]. 9 ABSTRACT: The reaction between 2-and 3-thienyl-substituted 1,3-butadiynes and the electron-deficient osmium cluster Os 3 H 2 (CO) 10 yields trinuclear coordination products, associated with transformations of the diacetylene ligands.…”

“…1.728 1.763 1.724 1.732 S(1)ÀC (18) 1.689( 6) 1.684 (8) 1.712 (7) 1.664 (5) 1.721 1.747 1.719 1.723 Os(2)ÀOs(1)ÀOs(3) 57.625 (7) indicating considerable delocalization. The C(12) vertex is identified as an sp 3 center bonded to two protons, which is in accordance with the 1 H NMR spectrum of 2.…”

Synthesis and molecular structures of phenylacetylide triosmium clusters

“…The l,g 2 - [3,5] and l 3 ,g 2 - [3,5,6] bonding types of the acetylenide ligand in triangular carbonyl clusters (including osmium) are the most widespread, the majority of these complexes also containing the bridging hydride ligands [3,5,[7][8][9][10][11]. Despite of a great volume of X-ray studies of acetylenide clusters a number of works on carbonyl clusters bearing only the bridging acetylenide and hydride ligands very limited, including only one X-ray study for acetylenide l,g 2 -bonding type [12] and few [5,7,10,11] for l 3 ,g 2 -type. Nevertheless, such model compounds are very convenient objects for study of dependence of the acetylenide ligand dynamic behavior on the cluster structure.…”

Reaction of the diyne complex [Os3(μ-CO)(CO)9{μ3-η2-Me3SiCCCCSiMe3}] with phosphines and phosphites: Characterization of monophosphine substituted clusters [Os3(μ-CO)(CO)8(PR3){μ3-η2-Me3SiCCCCSiMe3}] (PR3=PPh3, P(OEt)3, PEt3, PHPh2 and Ph2PCH2PPh2)

“…In reported reactions of diyne-substituted cluster complexes decarbonylation as well as ligand rearrangement paths can occur. In addition, in clusters where a free alkyne moiety is present, there is the possibility of carrying out further reactions with this fragment, as exemplified by the reaction of [Os 3 (l-CO)(CO) 9 (l 3 -g 2 -HC 2 C"CSiMe 3 )] with [Co 2 (CO) 8 ] where the complex [Os 3 (l-CO)(CO) 9 (l 3 -g 2 -HC 2 C 2 SiMe 3 ){Co 2 (CO) 6 }] was formed by coordination of the dicobalt fragment to the C"C triple bond adjacent to the SiMe 3 group [8]. When the ruthenium complex is used, a bow-tie cluster is formed by the insertion of the cobalt species into a Ru-Ru bond [9].…”