Acceptor CF3PCPH pincer reactivity with (PPh3)3Ir(CO)H

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 40; no. 39; pp. 10014 - 10019
• Main Authors: Adams, Jeramie J, Arulsamy, Navamoney, Roddick, Dean M
• Format: Journal Article
• Language: English
• Published: 01.01.2011
• Subjects: Benzene; Catalytic activity; Ligands; Oligomers; Prints; Refluxing
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/C1DT10952A

The syntheses of Ir(i) and Ir(iii) complexes incorporating the electron-withdrawing pincer ligand (1,3-C6H4(CH2P(CF3)2)2) (CF3PCPH) with (PPh3)3Ir(CO)H and subsequent chemistry are reported. Under ambient conditions, reaction of 1 equiv. CF3PCPH with (PPh3)3Ir(CO)H gave the mono-bridged complex [Ir(CO)(PPh3)2(H)]2([small mu ]-CF3PCPH) (1). Reaction of (PPh3)3Ir(CO)H with excess CF3PCPH and MeI gave the doubly-bridged complex [Ir(CO)(PPh3)(H)]2([small mu ]-CF3PCPH)2 (2), whereas the tetrameric oligomer [Ir(CO)(PPh3)(H)]4([small mu ]-CF3PCPH)4 (2-sq) was obtained from a 1 : 1 ligand : metal mixture in benzene in the presence of excess MeI. At higher temperatures (165 [degree]C) the reaction of CF3PCPH with (PPh3)3Ir(CO)H afforded the 5-coordinate Ir(i) complex (CF3PCP)Ir(CO)(PPh3) (3). Complex 3 shows mild catalytic activity for the decarbonylation of 2-naphthaldehyde in refluxing diglyme (162 [degree]C).