Dehydrohalogenation of Iodoarenes To Give Ruthenium Clusters Containing μ₄-Naphthyne and μ₄-Phenanthryne Ligands

Abstract

Iodobenzene and 4-iodotoluene react with [Ru3(CO)12] to give the oxidative addition products [Ru3(μ-I)(μ,η1:η6-C6H4R)(CO)8] (R = H, 4-Me), whereas 1-iodonaphthalene and 9-iodophenanthrene give the aryne clusters [Ru4(μ4,η2-L)(CO)12] (L = 1,2-naphthyne, 9,10-phenanthryne).

Nonrigid diastereomers: epimerization at chiral metal centers or chiral ligand conformations?

“…Notably, hindered phenyl rotation has been observed in BINAP complexes. [37][38][39] A specific blocking of rotation might bring this barrier higher. We believe this may occur in some Josiphos, 1-[(R)-2-(diphenylphosphino)ferrocenyl]ethyldi-t-butylphosphine, derivatives that we have made where a phenyl rotation may be blocked by the nearby ferrocenyl moiety.…”

Synthesis and structural characterization of ruthenium carbonyl clusters containing acetylenic fluorene moieties derived from 9-ethynylfluoren-9-ol

“…Cluster 4 exhibits five absorptions at 2070s, 2044vs, 2035w, 2010s and 1993w cm Ϫ1 in the IR spectrum (Table 1). Its 1 H NMR spectrum in CDCl 3 shows multiplets in the range δ 6.30-7.60 due to the seven protons on the phenyl rings and a singlet at δ 6.18 attributed to the methylene proton on C (14). Two upfield singlets at δ Ϫ3.00 and Ϫ10.00 were observed and assigned to the proton on the bridging hydroxyl group and the bridging hydride, respectively.…”

“…The C(15) atom of the fluorenyl group is bonded to Ru(4) in a σ fashion arising from the loss of the OH group. The ethynyl side chain [C(13)-C (14)] is activated to form two σ interactions with Ru(1) and Ru(2), and one π interaction with Ru(3). Moreover, as observed in 3, a µ 3 -hydroxide ligand bridging across Ru(1), Ru(3) and Ru( 4) is observed and it is also believed to originate from the hydroxyl group of 9-ethynylfluoren-9-ol.…”

“…The polyaromatic ligands in these structures exhibit a variety of bonding modes, e.g. metallacyclization in [Ru 2 (CO) 5 (µ-CO){µ-η 2 : η 4 -(C 6 H 4 ) 2 }], 10 face capping in [Ru 3 (CO) 7 (µ 3 -η 2 : η 3 : η 5 -C 12 H 8 )], 11 [Ru 7 C(CO) 16 (C 9 H 8 )] and [Ru 7 C(CO) 16 (C 12 H 12 )], 12 a phenylphosphido anthracene moiety with a bow-tie geometry in [Ru 5 (CO) 13 (µ 5 -η 1 : η 2 : η 3 : η 3 -C 14 H 8 -η 1 -PPh)], 13 a naphthyne ligand lying vertical to the Ru 4 metal plane in [Ru 4 (CO) 12 (µ 4 -η 2 -C 10 H 6 )] 14 and a chelating diphenylmethane moiety in [Ru 7 -C(CO) 14 (µ 3 -η 1 : η 6 : η 6 -C 6 H 4 CH 2 C 6 H 4 )]. 15 Compared to these polyaromatic ligands, the fluorenyl group which can be considered as a dibenzocyclopentadienyl system, has attracted relatively more attention from co-ordination chemists.…”

Exceedingly Facile PhX Activation (X=Cl, Br, I) with Ruthenium(II): Arresting Kinetics, Autocatalysis, and Mechanisms

“…Carbonyl-and PPh 3 -ligated Ru complexes can cleave the less inert C À Xb onds of iodo-and bromobenzene and -toluene, but only at 125 8 8C. [6] With bulky electron-rich Cy 3 Pco-ligands, Ru can activate the Ph À Ib ond at ambient temperature, [7a,b] but the ArÀCl bond requires 80 8 8C. [7c] In general, rutheniumcatalyzed arylation reactions with chloroarenes occur only at 120-150 8 8C.…”