Structural comparison of (pentamethylcyclopentadienyl)iridium(III) azido complexes containing potentially N,S-bidentate N-heterocyclic thiolates: 2- or 8-quinolinethiolate and benzimidazole-2-thiolate

Syntheses and crystal structures of mononuclear and dinuclear (pentamethylcyclopentadienyl)iridium(III) complexes containing 2-mercaptobenzimidazole

“…Compound 2 is a novel example in which both neutral H 2 bimt and monodeprotonated Hbimt À ligands are contained in a dinuclear complex; H 2 bimt binds two Ir III centers in a l-jS:jS fashion, while Hbimt À bridges asymmetrically in a l-jS:jN 1 mode. This bridging structure is similar to that observed in the analogous dinuclear azido complex, 3 [12], which contains two monoanionic Hbimt À ligands.…”

“…The Ir1-S1-C2, S1-C2-N1, and C2-N1-Ir2 bond angles are 105.9(2)°, 127.4(5)°, and 125.9(4)°, respectively, and the torsion angle of Ir1-S1-C2-N1 is 65.2(6)°. These structural parameters in the six-membered diiridacycle are comparable to those of the analogous azido complex 3, except for the remarkably smaller S1-Ir1-S2 bond angle (89.22(5)°in 3) [12]. The Ir1-Cl1 and Ir2-Cl2 bonds are 2.443(2) and 2.400(2) Å, respectively, which are typical for the Cp*Ir III -Cl complexes [19,20].…”

“…3), together with a PF 6 À anion, and two fully occupied and three half-occupied (positionally disordered) water molecules, [(Cp*IrCl) 2 (l-Hbimt)(l-H 2 bimt)]PF 6 Á3.5H 2 O (2). In a previous study, we have reported a similar dinuclear structure of the analogous azido complex, [{Cp*Ir(N 3 )} 2 (l-Hbimt-jS:jS)(l-Hbimt-jS:jN 1 )]ÁCH 3 OH (3) [12]. However, the azido complex 3 is neutral, while the present chlorido complex 2 is cationic.…”

“…In a previous study we have characterized a dinuclear iridium(III) complex bearing two Hbimt À ligands with different bridging modes, [{Cp*Ir(N 3 )} 2 (l-Hbimt-jS:jS)(l-Hbimt-jS:jN)]ÁCH 3 OH (3) {Cp* = g 5 -C 5 (CH 3 ) 5 } [12]. In this study we deal with two related ''Cp*Ir III Cl" complexes containing H 2 bimt and/or Hbimt À .…”

Iridium (III) and rhodium (III) triazoles by 1,3-dipolar cycloadditons to a coordinated azide in iridium (III) and rhodium (III) compounds

“…Keeping this in mind, we became interested in the synthesis of iridium and rhodium complexes of the type [(η 5 -Cp*)M(L ∩ L) N 3 ] and their cycloaddition reactions with alkynes. To the best of our knowledge, only one report has been given for the synthesis of Cp* iridium azido complex of the above-mentioned type, for example, [(η 5 -C 5 Me 5 )Ir(S ∩ N)(N 3 )] by Suzuki and coworkers (where S ∩ N = 2-quinolene thiolate) [26].…”