TY - JOUR
T1 - A specific formation of an iridium(III) hydrido complex bearing 8-(diphenylphosphino)quinoline
AU - Ariyoshi, Keita
AU - Kotera, Mai
AU - Namioka, Atsushi
AU - Suzuki, Takayoshi
N1 - Funding Information:
This work was supported in part by JSPS KAKENHI Grant Number 18K05146 .
Publisher Copyright:
© 2020 Elsevier Ltd
PY - 2020/3/15
Y1 - 2020/3/15
N2 - A reaction of [Cp*IrCl(Ph2Pqn)]PF6 {Cp* = η5-pentamethylcyclopentadienyl; Ph2Pqn = 8-(diphenylphosphino)quinoline} and Ag(CF3SO3) in methanol afforded orange crystals of the corresponding hydrido complex, [Cp*IrH(Ph2Pqn)]PF6, which was identified by 1H, 31P{1H} NMR and IR spectroscopy as well as X-ray structural analysis. The reactions in deuterated solvents indicated that formation of the hydrido complex proceeded via β-hydrogen elimination of the coordinated methanol molecule. It was also revealed that the hydrido formation was specific for the complex bearing Ph2Pqn ancillary ligand; the analogous complex with 1,2-bis(diphenylphosphino)benzene (diphos) or 1,10-phenanthroline (phen) did not give the corresponding hydrido complex by a similar reaction with Ag+ in methanol. In order to elucidate the reason for the different reactivity among these complexes, the crystal structures of the precursor chlorido complexes, [Cp*IrCl(Ph2Pqn)]PF6, [Cp*IrCl(diphos)]PF6 and [Cp*IrCl(phen)]PF6, as well as an acetonitrile complex of [Cp*Ir(Ph2Pqn)(CH3CN)](PF6)2, were also determined by X-ray analysis. The resulting structural information suggested that a specific formation of the hydrido complex with Ph2Pqn could be originated from the facile formation of the corresponding methanol complex and the hemilabile nature of ancillary Ph2Pqn ligand, which induced the reactivity of the coordinated methanol toward β-hydrogen elimination.
AB - A reaction of [Cp*IrCl(Ph2Pqn)]PF6 {Cp* = η5-pentamethylcyclopentadienyl; Ph2Pqn = 8-(diphenylphosphino)quinoline} and Ag(CF3SO3) in methanol afforded orange crystals of the corresponding hydrido complex, [Cp*IrH(Ph2Pqn)]PF6, which was identified by 1H, 31P{1H} NMR and IR spectroscopy as well as X-ray structural analysis. The reactions in deuterated solvents indicated that formation of the hydrido complex proceeded via β-hydrogen elimination of the coordinated methanol molecule. It was also revealed that the hydrido formation was specific for the complex bearing Ph2Pqn ancillary ligand; the analogous complex with 1,2-bis(diphenylphosphino)benzene (diphos) or 1,10-phenanthroline (phen) did not give the corresponding hydrido complex by a similar reaction with Ag+ in methanol. In order to elucidate the reason for the different reactivity among these complexes, the crystal structures of the precursor chlorido complexes, [Cp*IrCl(Ph2Pqn)]PF6, [Cp*IrCl(diphos)]PF6 and [Cp*IrCl(phen)]PF6, as well as an acetonitrile complex of [Cp*Ir(Ph2Pqn)(CH3CN)](PF6)2, were also determined by X-ray analysis. The resulting structural information suggested that a specific formation of the hydrido complex with Ph2Pqn could be originated from the facile formation of the corresponding methanol complex and the hemilabile nature of ancillary Ph2Pqn ligand, which induced the reactivity of the coordinated methanol toward β-hydrogen elimination.
KW - 8-Quinolylphosphine
KW - Ancillary ligand effect
KW - Hydrido complex
KW - Methanol complex
KW - β-Hydrogen elimination
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U2 - 10.1016/j.poly.2020.114401
DO - 10.1016/j.poly.2020.114401
M3 - Article
AN - SCOPUS:85078763167
VL - 179
JO - Polyhedron
JF - Polyhedron
SN - 0277-5387
M1 - 114401
ER -