Premium
Synthesis and Structural and Spectroscopic Characterization of New Ru II ‐dmso Precursors with Face‐Capping Ligands for Use in Self‐Assembly Reactions
Author(s) -
Iengo Elisabetta,
Zangrando Ennio,
Baiutti Edi,
Munini Fabio,
Alessio Enzo
Publication year - 2005
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.200400717
Subject(s) - chemistry , ligand (biochemistry) , ruthenium , medicinal chemistry , octahedron , trifluoromethanesulfonate , stereochemistry , crystallography , crystal structure , catalysis , organic chemistry , biochemistry , receptor
The aim of this work is the preparation of new, easy‐to‐make, octahedral Ru II precursors with facial geometry to be used in self‐assembly reactions. We chose dmso as a leaving group and 1,4,7‐trithiacyclononane ([9]aneS 3 ), tris(pyrazolyl)methane [CH(pz) 3 , pz = pyrazol‐1‐yl], or triphos [CH 3 C(CH 2 ‐PPh 2 ) 3 ] as the face‐capping ligand (fcl). We describe here the preparation and structural characterization of three new dicationic Ru II complexes (as triflate salts) of the type fac ‐[Ru(fcl)(solv) 3 ] 2+ , namely fac ‐[Ru([9]aneS 3 )(dmso‐O)(dmso‐S) 2 ] 2+ ( 3b ), which equilibrates in solution with the linkage isomer fac ‐[Ru([9]aneS 3 )(dmso‐O) 2 (dmso‐S)] 2+ ( 3a ), fac ‐[Ru{CH(pz) 3 }(dmso‐O)(dmso‐S) 2 ] 2+ ( 7 ), and fac ‐[Ru(triphos)‐(dmso‐O) 2 (H 2 O)] 2+ ( 9 ). In all cases the preferred synthetic procedure involved coordination of the face‐capping ligand to cis ‐[RuCl 2 (dmso) 4 ] first, followed by replacement of the chlorides with dmso (or water) molecules assisted by addition of AgCF 3 SO 3 (AgOTf). NMR investigations showed that hydrolysis of the dmso ligands occurs very easily for 3 in water and for 9 in chloroform, while for complex 7 only the O‐bound dmso ligand is replaced in water. In the course of this work, the following complexes were also isolated and structurally characterized: fac ‐[Ru([9]aneS 3 )Cl(dmso‐S) 2 ][OTf] ( 2 ), trans , cis , cis ‐[RuCl 2 (dmso‐S) 2 {CH(pz) 2 (pz)}] ( 4 ), trans , cis , cis ‐[RuCl 2 (dmso‐S) 2 (pzH) 2 ] ( 5 ), fac ‐[Ru{CH(pz) 3 }Cl 2 (dmso‐S)] ( 6 ), fac ‐[Ru([9]aneS 3 )(py) 3 ][OTf] 2 ( 11 ), fac ‐[Ru([9]aneS 3 )(py) 2 ‐(CH 3 CN)][OTf] 2 ( 13 ), and fac ‐[Ru([9]aneS 3 O)(dmso‐O) 2 ‐(dmso‐S)][OTf] 2 ([9]aneS 3 O = 1,4,7‐trithiacyclononane 1‐oxide); in 4 the tripodal tris(pyrazolyl)methane acts as a bidentate ligand. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)