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Metalloligands: Rhodium(III) Cyclometallated Compounds Containing Multitopological Binucleating Ligands
Author(s) -
Lanza Santo,
Giannetto Antonino,
Bruno Giuseppe,
Nicolò Franco,
Tresoldi Giuseppe
Publication year - 2009
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200900165
Subject(s) - chemistry , rhodium , medicinal chemistry , bimetallic strip , isopropyl , ligand (biochemistry) , stereochemistry , isoamyl alcohol , catalysis , organic chemistry , receptor , biochemistry , alcohol
The reaction of [Rh(2‐phenylpyridine) 2 Cl] 2 with secondary dithiooxamides H 2 R 2 C 2 N 2 S 2 (R = isoamyl, isopropyl, {S}‐phenylethyl, meso ‐phenylethyl) affords the contact ion pair [Rh(2‐phenylpyridine) 2 (H 2 R 2 C 2 N 2 S 2 κ‐ S , S ‐Rh)] + Cl – , which can be transformed into the neutral complexes [Rh(2‐phenylpyridine) 2 (HR 2 C 2 N 2 S 2 κ‐ S , S ‐Rh)]. The HCl exchange between the ion pairs and the corresponding neutral complexes has been studied by means of dynamic NMR spectroscopy techniques, and a mechanism for this exchange has been proposed. [Rh(2‐phenylpyridine) 2 {H(isoamyl) 2 C 2 N 2 S 2 κ‐ S , S ‐Rh}] reacts with chlorido‐bridged dimers [ML n Cl] 2 {ML n = Pd(η 3 ‐allyl), Rh(cyclooctadiene), ( n ‐propyl) 3 PClPd} and provides the heterobimetallic complexes [Rh(2‐phenylpyridine) 2 {μ‐(isoamyl) 2 C 2 N 2 S 2 }ML n ]. Heterobimetallic complexes having the same formula and the same structure are obtained by reaction of [ML n {H(isoamyl) 2 C 2 N 2 S 2 κ‐ S , S ‐M}] species [ML n = Rh(1,5‐cyclooctadiene), Pd(η 3 ‐allyl), PdCl(tri‐ n ‐propylphosphane), PtCl(diphenyl‐2‐pyridylphosphane)] with [Rh(2‐phenylpyridine) 2 Cl] 2 . The connectivity of the binucleating ligand diisoamyldithiooxamidate within the bimetallic complexes has been assessed. The linkage isomer obtainedis [Rh(2‐phenylpyridine) 2 {μ‐(isoamyl) 2 C 2 N 2 S 2 }ML n ] (κ‐ N , N ‐Rh III , κ‐ S , S ‐M).(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)