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Ring Slippage and Dissociation of Pentamethylcyclopentadienyl Ligand in an (η5-Cp*)Ir Complex with a κ3-O,C,O Tridentate Calix[4]arene Ligand under Mild Conditions by Takuya Kuwabara; Ryogen Tezuka; Mikiya Ishikawa; Takuya Yamazaki; Shintaro Kodama; Youichi Ishii is a Chemistry article available to read on EtoBox.

What is Ring Slippage and Dissociation of Pentamethylcyclopentadienyl Ligand in an (η5-Cp*)Ir Complex with a κ3-O,C,O Tridentate Calix[4]arene Ligand under Mild Conditions about?

The first examples of κ 3 -O,C,O tridentate calix[4]arene transition-metal complexes [Cp\*M(p-t Bucalix[4]arene-(2-)-κ 3 -O,C,O)] (M = Ir, Rh) that are stable both in the solid state and in solution were synthesized. The reaction of the Ir complex with 2 equiv of xylyl isocyanide afforded the (η 1 -Cp\*)Ir(CNXy) 2 complex in which the Cp\* ligand is slipped from an η 5 to an η 1 fashion, although ring slippage of an η 5 -Cp\* ligand is very uncommon in comparison with that of Cp. The reaction of the (η 1 -Cp\*)Ir complex with additional 1 equiv of isocyanide resulted in the liberation of the Cp\* ligand as Cp\*H, which was confirmed by 1 H NMR. This study provides the first observation of stepwise dissociation of a Cp\* ligand from group 4-10 transition-metals via η 1 coordination. This unique phenomenon seems to be facilitated by flexible coordination of an OH group in the C-metalated calix[4]arene ligand. C yclopentadienyl anion (C 5 H 5 ; Cp) has played a central role as a ligand for transition-metal complexes since the discovery of the first sandwich complex, ferrocene (Cp 2 Fe). 1 Cp complexes have been widely investigated in various fields including catalytic chemistry, 2 mat

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Author

Takuya Kuwabara; Ryogen Tezuka; Mikiya Ishikawa; Takuya Yamazaki; Shintaro Kodama; Youichi Ishii

Published

2018

Language

EN

Field

Chemistry (Physical Sciences)