Mono(2,2′‐bipyridyl)Ru ^{IIII Complex with Four Dimethyl Sulfoxide Ligands as Precursor for ciscis ‐Bis‐heteroleptic Ru IIII Complex: Syntheses, Structures, and Substitution Reactions}

摘要

> The dication complex trans (O,S)‐[Ru(bpy)(dmso‐ O ) ₂ (dmso‐ S ) ₂ ](OTf) ₂ [ 1· (OTf) ₂ ; bpy = 2,2′‐bipyridyl; dmso = dimethyl sulfoxide; OTf – = CF ₃ SO ₃ – ] was obtained from the reaction of cis (Cl), cis ( S )‐[RuCl ₂ (bpy)(dmso‐ S ) ₂ ] with Ag(OTf) in DMSO. The crystal structure of 1· (OTf) ₂ revealed two labile dmso‐ O ligands and two less‐labile dmso‐ S ligands positioned cis to each other. In DMSO, the equatorial dmso‐ O in 1 2+ equilibrates with its linkage isomer dmso‐ S to fac ( S )‐[Ru(bpy)(dmso‐ O )(dmso‐ S ) ₃ ] 2+ [ 1 _iso 2+ ] ([ 1 _iso 2+ ]/[ 1 2+ ] = 3:97 at 298 K and 33:67 at 373 K). The linkage isomerization kinetic parameters, deter min ed by 1 H NMR, were Δ H = 22(1) kJ?mol