Codimerisation of CO and a 1,3-diynyl–metal complex on an Ru₃cluster

Attaching Metal-Capped sp Carbon Chains to Metal Clusters: Synthesis, Structure, and Reactivity of Rhenium/Triosmium Complexes of Formula [(η5-C5Me5)Re(NO)(PPh3)(CC)nOs3(CO)y(X)z]m+, Including Carbon Geometries More Distorted than Planar Tetracoordinate

“…[15] Surprisingly, to our knowledge no adducts analogous to the Re(CC) n Os 3 species 2, 4, or 6 have been described previously. Recently, reactions of terminal alkynes and a low-temperature Ru 3 -(CO) 11 [18] When refluxed in benzene, 11 decarbonylates to the WC 4 Ru 3 (CO) 9 (H) complex 12, which is analogous to the ReC 4 Os 3 (CO) 9 (H) complex 7 obtained by the thermolysis of 4 in Scheme 1. In principle, a tungsten/triruthenium complex sim- ilar to 4 might be on the reaction coordinate between 11 and 12.…”

“…[3b, 18] Hence, the structure in Scheme 2 is highly probable. Also, 7 gave an IR n Ä NO band (1663 cm À1 ) near those of 2, 4, and 6.…”

Synthesis, characterization and reactivity studies of the new compound [Os3(CO)9(μ3-η2,η3,η3-{C5H5FeC5H3CCC(S)C(Fc)CHO}]

“…The scarce examples of aldehyde oxametallacycle derivatives reported have been obtained in situ towards different reaction processes. Thus, compound [Os 3 (CO) 10 (l-H)(l 3 ,g 2 -CHC(O)H)] [9] has been detected in a 1 H NMR experiment from the reaction between Os 3 (CO) 10 (l-H) 2 and 1-pentyne and a WRu 3 cluster containing an aldehyde oxametallacycle has been obtained from the reaction of [Ru 3 (CO) 10 (NCMe) 2 ] and [W(C"CC"CH)(CO) 3 Cp] [10].…”

“…Thus, conversion of two FcC"CSC"CSiMe 3 molecules into the new dithioether SiMe 3 CC(C 2 Fc)SC(Fc)CSCCSiMe 3 by formation of a new S-C bond, has been confirmed in the preparation of the compound [Ru 3 (CO) 9 {l 3 -g 2 ,g 4 ,g 3 -Me 3 SiCC(C 2 Fc)SC-(Fc)CSCCSiMe 3 }] [1d], while the triosmium derivative [Os 3 (CO) 9 (l 3 -g 2 ,g 3 ,g 3 -{C 5 H 5 FeC 5 H 3 CCC(S)C(SiMe 3 )-CHO}] [1f] containing the CHO end-capping thiolate C 5 H 5 FeC 5 H 3 CCC(S)C(SiMe 3 )CHO has been obtained in the osmium case. On the basis of these results, we considered it to be of interest to explore the reactivity of the compound FcC"CSC"CFc with the activated cluster [Os 3 (CO) 10 (NCMe) 2 ]. These results are herein described.…”

“…Selected bond distances (Å ) and angles (°). C(1)-O(1) 1.270(10), C(12)-Os(1) 2.137(8), O(1)-Os(1) 2.179(6), Os(2…”