501119-41-1Relevant articles and documents
Reactions of bis[dichloro(pentamethylcyclopentadienyl)rhodium(III) and -iridium(III)] with aromatic phosphine bearing a methoxy group at an ortho-position: Double insertion of 1-alkynes into a Rh-O bond
Yamamoto, Yasuhiro,Sugawara, Kenichiro,Kakeya, Masateru
, p. 21 - 28 (2008/10/08)
Reactions of [Cp*MCl2]2 (1a: M = Rh, 1b: M = Ir; Cp* = C5Me5) with 2-methoxyphenylphosphines at room temperature gave the corresponding 1η-P coordination complexes, [Cp*MCl2(PPh3-nRn)] (2: n = 1; 4: n = 2; 6b: n = 3 for R = C6H4-2-MeO). Reaction of 1 with (2-methoxyphenyl)diphenylphosphine at reflux in diglyme underwent demethylation to afford Cp*MCl(MMMPP-P,O) (3) (M = Rh, Ir; MMMPP-P,O = PPh2(C6H4-2-O)) with a (P,O) chelating ligand. In the reaction with bis(2-methoxyphenyl)phenylphosphine, Cp*MCl(BMMPP-P,O) (5) (M = Rh, Ir; BMMPP-P,O = PPh(C6H4-2-MeO)(C6H4-2-O)) was generated at reflux in a mixture of diglyme and MeOH. Tris(2-methoxyphenyl)phosphine reacted with 1a at reflux in MeOH to give Cp*RhCl(TMMPP-P,O) (7a) (TMMPP-P,O = P(C6H4-2-MeO)2(C6H 4-2-O)), whereas the reaction with 1b at reflux in EtOH generated Cp*Ir(TMMPP-P,O,O′) (8b) (TMMPP-P,O,O′ = P(C6H4-2-MeO)(C6H4-2-O) 2) with a (P,O,O′) tridentate ligand. Crystal structural analyses of 3a, 5a and 8b were carried out. Complex 3a underwent a double insertion of alkyne into a Rh-O bond on treatment with phenylacetylene or p-tolylacetylene in the presence of KPF6, giving [Cp*Rh{PPh2(C6H4-O-CR=CH-CH=CR}](PF 6) (9a: R = p-MeC6H4; 9b: R = Ph) with a (P,O,C) tridentate ligand, in which X-ray crystal analysis of 9a was performed.
