228551-59-5Relevant academic research and scientific papers
Reactions of bis[dichloro(η5-pentamethylcyclopentadienyl)iridium(III)] with bulky and highly basic aromatic phosphines containing ortho-methoxy groups
Yamamoto, Yasuhiro,Kawasaki, Keisuke,Nishimura, Saho
, p. 49 - 57 (2007/10/03)
Reaction of [Cp*IrCl2]2 1 (Cp=C5Me5) with (2,6-dimethoxyphenyl)diphenylphosphine (MDMPP) at room temperature gave a monohapto-complex [Cp*IrCl2(MDMPP-P)] 2a, whereas the reaction with bis(2,6-dimethoxyphenyl)phenylphosphine (BDMPP) led to loss of one molecule of CH3Cl to give Cp*IrCl[P(C6H3-2-O-6-OMe){C6H 3-2,6-(MeO)2} Ph] (=Cp*IrCl(BDMPP-κ2P,O) 3b with a chelated P,O coordination, in which the structure was confirmed by an X-ray analysis: a=15.994(3) A, b=10.471(2) A, c=17.727(3) A, β=94.12(1)°, monoclinic, P21/n, Z=4, R=0.032. Tris(2,6-dimethoxyphenyl)phosphine (TDMPP) reacted with 1 to afford Cp*Ir[P(C6H3-2-O-6-OMe)2{C 6H3-2,6-(MeO)2}] (=Cp*IrCl(TDMPP-κ3P,O,O′) 4c. It was confirmed by an X-ray analysis that the molecule has a trihapto coordination (P,O,O′) derived from demethylation of two molecules of CH3Cl: a=17.55(1) A, b=21.22(3) A, c=15.92(2) A, orthorhombic, Pbcn, Z=8, R=0.044. Complex 1 was treated with MDMPP, BDMPP or TDMPP in acetone in the presence of a PF6 anion to give salt-like complexes [Cp*IrCl(XDMPP-κ2P,OMe)][PF6] 5 (X=M, B, T) with a P,O coordination. The structures of 5b and 5c·CHCl3 were confirmed by X-ray analyses: for 5b (X=B), a=11.679(2) A, b=15.389(4) A, c=10.251(3) A, α=103.92(2)°, β=91.76(2)°, γ=105.15(2)°, triclinic, P1, Z=2, R=0.046; for 5c·CHCl3 (X=T), a=14.730(7) A, b=18.55(2) A, c=15.753(9) A, β=91.76(2)°, γ=105.45(5)°, monoclinic, P21/n, Z=4, R=0.048. In complexes 5a and 5b the exchange between free and coordinated OMe groups was observed, whereas in 5c such exchange was not observed. Complex 2a readily reacted with Lewis bases (L) such as isocyanide and CO in the presence of a PF6 anion to produce [Cp*IrCl(L)(MDMPP-P)][PF6] 6.
