The synthesis and characterization of three novel ferrocenylphosphino sulfonates, namely ( 5-C 5 H 3 PR 2 (SO 3 i-Pr))Fe( 5-C 5 H 5) (R = Ph, p-Tol, Cy), is presented along with their solid-state X-ray crystal structures. Preliminary studies on the utility of these compounds as auxiliary ligands in aqueous catalysis, in particular for the rutheniumcatalyzed ortho-arylation of 2-phenylpyridine, are also discussed.
The new rhenium complexes (eta(5)-C(5)H(4)PPh(2))Re(CO)(2)(PR(3)) (R = Me (1) and OMe (2)) were prepared photochemically from (eta(5)-C(5)H(4)PPh(2))Re(CO)(3) in the presence of PMe(3) or P(OMe)(3). Further reaction of these ligands with PdCl(2)(NCPh)(2) in chloroform, produces the heterobimetallic complexes (CO)(2)(PMe(3))(eta(5)-C(5)H(4)PPh(2))Re-PdCl(2) (3) and (CO)(2)(P(OMe)(3))(eta(5)-C(5)H(4)PPh(2))Re-PdCl(2) (4). IR spectroscopy reveals that both complexes possess a Re-Pd interaction which was confirmed by X-ray crystallography (Re-Pd bond distance = 2.762 A in and 2.774 A in ). Relativistic functional density theory calculations have also been carried out in order to probe the bonding in these compounds.
The synthesis and characterization of novel gold(I) complexes containing hydrophilic ferrocenylphosphino sulfonate ligands, i.e., compounds [AuCl{(η5-C5H3PR2(SO3iPr))Fe(η5-C5H5)}] (R = Ph (2a), p-Tol (2b), Cy (2c)), are presented, including a single-crystal X-ray diffraction study on 2a. Complexes 2a–c were checked as catalysts for the intermolecular addition of carboxylic acids to nonactivated internal alkynes using water as a green reaction medium. The best results in terms of activity were obtained with 2a in combination with AgOAc, which was able to promote the selective anti addition of a variety of aromatic, aliphatic, and α,β-unsaturated carboxylic acids to both symmetrical and unsymmetrical internal alkynes at 60 °C, employing metal loadings of only 2 mol %.
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