Synthesis, Characterization, and Reactivity Study of Triosmium Acetylide Cluster Complexes Bearing a (C₅Me₅)W(O)₂Fragment

Abstract

The heterometallic cluster compound (C5Me5)W(μ-O)2Os3(μ-CCPh)(CO)9 (1), which possesses two edge-bridging oxo groups and an acetylide ligand in a μ-η2 mode, has been obtained by addition of (C5Me5)W(O)2(CCPh) to Os3(CO)10(NCMe)2. The subsequent reactivity studies led to the isolation of Cp*W(μ-O)2Os3(μ-H)(CO)9 (2) and Cp*W(O)(μ-O)Os3(CCPh)(CO)9 (3) through hydrogenation and treatment with pressurized CO, respectively. The structures of 1 and 3 reveal two distinctive bonding modes for the (C5Me5)W(O)2 fragment on an Os3 skeleton.

Alkyne−Acetylide Coupling in Cluster Compounds Bearing a Triosmium Carbonyl Os3(CO)8 Fragment and a High Oxidation State (C5Me5)W(O)2 Unit

“…In this paper, we describe the addition of alkynes to a target cluster Cp*WOs 3 (μ-O) 2 (CCPh)(CO) 9 , Cp* = C 5 Me 5 , prepared from addition of Cp*W(O) 2 (CCPh) to Os 3 (CO) 10 (NCMe) 2 (Scheme ) and the subsequent C−C bond formation between ligated acetylide and alkyne in its coordination sphere. An additional feature of this chemistry is a facile change in the bonding capability of the Cp*W(O) 2 fragment which occurs during the transformation.…”

Synthesis and X-ray Structures of [Os3Pt(CO)9(μ4-η2-C≡CPh)(η1-C≡CPh)(L)] (L = 4,4′-Dimethyl-2,2′-bipyridine, 4,4′-bis(tert-butyl)-2,2′-bipyridine): New Heterometallic Clusters with a μ4-η2- and an η1-Acetylide Group on a Spiked-Triangular Metal Core

“…The presence of an η 1 ‐acetylide ligand is a relatively rare phenomenon in osmium cluster chemistry, although terminal acetylides are common in mononuclear osmium complexes 23−25. A similar feature is only found in the homometallic [Os 3 (CO) 6 (μ‐η 2 ‐C≡CPh)(η 1 ‐C≡CPh)(μ‐PPh 2 ) 2 (NH 2 Et) 2 ]26 and the heterometallic [(η 5 ‐C 5 Me 5 )W(O)(μ‐O)Os 3 (η 1 ‐C≡CPh)(CO) 11 ]27 complexes.…”

High oxidation state organomolybdenum and organotungsten chemistry in protic environments

“…The organic ligands in these compounds are on the Rh or Ru atoms, whereas the high oxidation state Mo or W centres are inorganic. Other condensation processes using high oxidation state organometallic Group 6 metal complexes and other reagents have been conducted in anhydrous media, for instance the reaction between [Cp * WO 2 (C CPh)] and [Ru 4 (CO) 13 ( 3 -PPh)] in refluxing toluene yields mainly [(Cp * WO 2 )Ru 4 (CO) 10 ( 4 -PPh)(C CPh)] with small amounts of [(Cp * WO 2 )Ru 4 (CO) 7 (C 7 H 8 )( 4 -PPh)(C CPh)] and [(Cp * WO 2 )Ru 5 (CO) 12 (C 7 H 8 )( 4 -PPh)(C CPh)] [172], whereas the same W complex reacts with [Os 3 (CO) 10 (MeCN) 2 ] to yield [(Cp * WO 2 )Os 3 (CO) 9 (C CPh)] [173].…”