Reactions of (η⁶:η¹-C₆H₅CH₂CH₂PR₂)Ru(CH₃)₂ (R = Cy, Ph) with [H(Et₂O)₂][B(3,5-C₆H₃(CF₃)₂)₄] in the Presence of Carbon Monoxide, Acetylene, Ethylene, and Norbornene

Abstract

The reactions of (η 6 :η 1 -C 6 H 5 CH 2 CH 2 PR 2 )Ru(CH 3 ) 2 , where R ) Cy (1), Ph (2), with boron activators in the presence of CO, acetylene, ethylene, and norbornene were explored. The reaction of 1 and 2 with H( and 4, respectively). The reaction of 1 and 2 with H + Bin the presence of acetylene afforded polyacetylene and [(η 6 -C 6 H 5 -CH 2 CH 2 PR 2 )Ru(η 3 -CH 3 CHC 5 H 5 )][B(3,5-C 6 H 3 (CF 3 ) 2 ) 4 ] (5 and 6, respectively). The latter reactions were proposed to proceed via coordinative insertion of acetylene into Ru-alkyl bonds. In contrast, the reaction of 2 with H + Bin the presence of ethylene initially afforded the precursor complex [(η 6 :η 7). Finally, the reaction of 1 and 2 with H + Bin the presence of excess norbornene afforded ring-opened polynorbornene, presumably via Ru-catalyzed ring-opening metathesis polymerization (ROMP). The reaction products were characterized by IR and NMR spectroscopy. Single-crystal X-ray structural analyses of complexes 3, 5, 6, and 7 were also performed.

Synthesis and alkyne-coupling chemistry of cyclomanganated 1- and 3-acetylindoles, 3-formylindole and analogues

“…For the allyl group the exocyclic C(8)-C(9) bond is significantly longer, 1.442(6) Å, than the internal one C(9)-C(10), 1.376(6) Å, with the manganese atom closest to the external carbon atom. This is a similar pattern to that observed in the related ruthenium compound 10 where again the cyclopentadiene-allyl ligand was formed in situ by trimerisation of acetylene [14].…”

p-Cymene ruthenium thioether complexes

“…This reaction provides an easy access to tethered complexes where the phosphine substituted arene serves as an eight electron donor chelate ligand. Some of these complexes display reactivities that markedly differ from those of their non-tethered analogs [28,29]. In contrast, no such arene substitution was observed for complexes 2a,b even in hot chlorobenzene.…”

Tethering versus Non‐Coordination of Hydroxy and Methoxy Side Chains in Arene Half Sandwich Dichloro Ruthenium Complexes

“…1.496(7) C91 -091/C92-092 1.422(10)/1.436 (10) Arene;' 1 = midpoinl of lhe arene ring taining to the data collection and structure solution are collected in Table I . Table 2 provides important bond lengths 402 and angles.…”

“…While the 3-hydroxypropylbenzene derived complex Ib is somewhat easier to oxidize than its methyl ether 2b, the opposite holds for the PCY3 complexes le, 2e. Table 3 Redox potentials of the complexes; peak-to-peak separations are given in parantheses a) +0.775 (77) a) potentials are provided relalive to the Fe/Fe ' sea le; 10) at 196 K; c ) irreversible red uelion peak; d) irreversible anodic peak following reduetion; c ) irreversible anodie peak following reduclion in the presenee of NaSbF 6 ; f) irreversible cathodie peak followin g oxidation.…”

“…Arene displacement in complexes [(Tj 6-arene)RuCI2{PRiCHz)naryl}] is then achieved by an either thermally [I , 2,4,8] or oxidatively induced substitution step [I]. These studies have a lso disclosed, that tethered coordinating groups may endow such complexes with reactivities that difTer significantly from their non-tethered congeners [10,11]. M uch less work has been done on com- Pfa fTenwaldring 55 0-70569 Stuttgart 400 chloride ligand of one and the coordinated hydroxy group of a neigh bour molecule, resulting in a sheet structure.…”