Mercury–osmium carbonyl clusters resulting from facile Hg–C bond cleavage: reactions of [Os₃H₂(CO)₁₀] with [Hg(CCPh)₂] and [RHgCCHgR](R = Ph, Me or Et)

Abstract

Reaction of the unsaturated cluster [Os,H,(CO),,] with Hg(C=CPh), afforded two new 0s-Hg clusters cis-[Os(CO), ((p-Hg)Os,(CO),o(p-q2-CH=CHPh))2] 1 and [(OS,(CO),,(~-~~-CH=CHP~))~(~~-H~)] 2 in 30 and 20% yield, respectively. Cluster 1 consists of two (p-Hg)Os,(CO),,(p-q2-CH=CHPhj subunits bonded to a 1

Rearrangement or C−H Activation Processes Promoted by Reaction with the Solvate [cis-Pt(C6F5)2(thf)2]

“…As far as we know, this structural feature has no precedent in the literature, the most similar examples being a (μ-hydroxy)(μ-alkyne) bridging system in a pentanuclear ruthenium cluster and a (μ-hydroxy)(μ-allenylidene) trinuclear osmium cluster . Notwithstanding, a good number of vinyl groups acting as bridging ligands between two transition metals have been reported, − although the examples containing platinum are really scarce, − in particular, those referring to homopolynuclear derivatives. ,, It should be noted that recently a (μ-hydride)(μ-vinyl) dinuclear intermediate species has been proposed in the formation of the (μ-alkylidene) complex [Pt 2 (dppm) 2 (μ-H)(μ-CHCH 2 Ph)](BF 4 ) 5 ORTEP view of [ cis,cis -(PPh 3 ) 2 Pt{μ-1κ C α :η 2 -CHCHC(OH)Ph 2 }(μ-OH)Pt(C 6 F 5 ) 2 ] ( 5f ).…”

The Interplay of Bis(tricarbido) and Dimetallaoctatetrayne Complexes of Platinum

“…There is limited precedent for the use of alkynylmercurials as alkynyl transfer reagents for lanthanides and transition metals ,,, including those of group 10 . We have therefore investigated the reactions of the bis(tricarbido)mercurial 2 and the isoelectronic aurate PPN[Au{CCCW(CO) 2 (L)} 2 ] (PPN[ 3 ]) toward phosphine complexes of platinum(0) and (II), which again demonstrate a subtle interplay between the bis(tricarbido) vs dimetallaoctatetrayne structures, which is itself distinct from that observed for earlier transition metals.…”

Reactivity of the Unsaturated Hydride [Mo2(η5-C5H5)2(μ-H)(μ-PCy2)(CO)2] toward 17- and 16-Electron Metal Carbonyl Fragments: Rational Synthesis of Electron-Deficient Heterometallic Clusters

“…Extensive studies have also been carried out with the isoelectronic dirhenium complex [Re 2 (μ-H) 2 (CO) 8 ], which reacts easily with different transition-metal complexes such as the metal carbonyl anions [M(CO) x ] - (M = Mn, Re, Ir; x = 4, 5) and [Re 2 H(CO) 9 ] - 8a,9 or the neutral late transition-metal compounds [Pt(PPh 3 ) 2 (C 2 H 4 )], [Pt(COD) 2 ], or [Ir(CO)(η 5 -C 9 H 7 )(η 2 -C 8 H 14 )], to give new tri- or tetranuclear clusters. Finally, the reactivity of the triosmium dihydride [Os 3 (μ-H) 2 (CO) 10 ] toward organometallic fragments has been also widely studied, allowing the synthesis of heterometallic clusters with higher nuclearity and incorporating transition-metal atoms from groups 6, , 8, − 9, − 10, 19a, 11, 19a, and 12 …”