Acceptor (PCPH)-P-CF3 pincer reactivity with (PPh3)(3)Ir(CO)H

作者：Adams Jeramie J; Arulsamy Navamoney; Roddick Dean M^*

来源：Dalton Transactions, 2011, 40(39): 10014-10019.

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)(3)Ir(CO) H and subsequent chemistry are reported. Under ambient conditions, reaction of 1 equiv. (PCPH)-P-CF3 with (PPh3)(3)Ir(CO) H gave the mono-bridged complex [Ir(CO)(PPh3)(2)(H)](2)(mu-(PCPH)-P-CF3) (1). Reaction of (PPh3)(3)Ir(CO) H with excess (PCPH)-P-CF3 and MeI gave the doubly-bridged complex [Ir(CO)(PPh3)(H)](2)(mu-CF3PCPH)(2) (2), whereas the tetrameric oligomer [Ir(CO)(PPh3)(H)](4)(mu-(PCPH)-P-CF3)(4) (2-sq) was obtained from a 1 : 1 ligand : metal mixture in benzene in the presence of excess MeI. At higher temperatures (165 degrees C) the reaction of (PCPH)-P-CF3 with (PPh3)(3)Ir(CO) H afforded the 5-coordinate Ir(I) complex ((PCP)-P-CF3) Ir(CO)(PPh3) (3). Complex 3 shows mild catalytic activity for the decarbonylation of 2-naphthaldehyde in refluxing diglyme (162 degrees C).

• 出版日期2011