Synthesis, structural characterization and solution dynamics of osmium–rhodium mixed-metal cluster [Os4Rh(μ-H)4(CO)13(η2-NC5H4C2H2)]

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 ).…”

Cyclometalation of 2-Vinylpyridine with MCl2(PPh3)3and MHCl(PPh3)3(M = Ru, Os)

“…Cyclometalation reactions of 2-vinylpyridine have been reported previously with metal complexes of Pd, Pt, Ir, Rh, − Co, Re, , Ru − and Os. ,− In the cases of ruthenium and osmium, cyclometalation of 2-vinylpyridine has been observed in the reactions of 2-vinylpyridine with complexes such as RuH 4 (PhP(CH 2 CH 2 CH 2 PCy 2 ) 2 ), [RuHCl(P i Pr 3 ) 2 ] 2 , Ru(R)Cl(CO)(P i Pr 3 ) 2 (R = Ph, CHCHPh), Os(R)Cl(CO)(P i Pr 3 ) 2 (R = Ph, CHCHPh), Os 3 (CO) 10 (MeCN) 2 , OsH 6 (P i Pr 3 ) 2 , OsH 2 Cl 2 (P i Pr 3 ) 2 , 26 and OsH 3 (SnPh 2 Cl)(CH 2 CHP i Pr 2 )(P i Pr 3 ) . However, the reactions of MCl 2 (PPh 3 ) 3 and MHCl(PPh 3 ) 3 (M = Ru, Os) with 2-vinylpyridine have not been reported, despite the fact that RuCl 2 (PPh 3 ) 3 is known to promote the coupling reactions of 2-alkenylpyridines with aryl bromides (the Heck reaction), for which cyclometalation of C−H bonds of alkenylpyridines on a Ru(II) or Ru(0) center has been suggested as one of the key steps …”