Portal de Periódicos da CAPES

Reactivity of ketonylgold(III) complexes. Crystal and molecular structure of SP-4-4-[Au(2-C6H4N2Ph){CH2COC6H2(OMe)3-3,4,5} Cl(PPh3)] and SP-4-4-[Au(2-C6H4N2Ph)(CH2COMe)Cl(PPh3)]

1993; Elsevier BV; Volume: 456; Issue: 2 Linguagem: Inglês

10.1016/0022-328x(93)80441-d

1872-8561

José Vicente, María-Dolores Bermúdez, María-Pilar Carrillo, Peter G. Jones,

Catalytic Alkyne Reactions

Ketonyl complexes [Au(η2-pap)(η1-CH2COR)Cl][η2pap = 2-(phenylazo)phenyl-C1,N2′] react i) with various salts [AgAc, Ac = MeCO2, or NaI] to give neutral complexes [Au(η2-pap)(η1-CH2COMe)X][X = Ac (1), I (2)], ii) with PPh3 to give [Au(η1-pap)(η1- CH2COR)Cl(PPh3)] (R = Me (3), C6H2(OMe)3-3,4,5 (4)], iii) with PPh3 and KCN to give [Au(η1-pap)(η1-CH2COMe)CN(PPh3)] (5), iv) with Ph2P(CH2)2PPh2 (dppe) (1:1) to give [Au(η1-pap)(η1-CH2COMe)(μ-dppe)]2 Cl2 (6a) which in turn reacts with NaClO4 to give [Au(η1-pap)(η1-CH2COMe)(μ-dppe)]2 (ClO4)2 (6b), v) with PhNH2 to give [Au(η2-pap){η1-CH2C(=NPh)Me}Cl] (7), or vi) with AgClO4 or Ag(CF3SO3) to give [Au(η2-pap)(η2-CH2COMe)]X [X = ClO4 (8a), CF3SO3 (8b)]. The complex [Au(η1-pap)(η1-CH2COMe)Cl(PPh3)] shows dynamic behaviour in solution. Low-temperature crystal structures have been determined for complexes 3 and 4. 3 crystallizes in the triclinic space group P1 with a = 10.389(3), b = 11.269(3), c = 14.482(3), α = 89.20(2), β = 72.95(2), γ = 63.43(2)°, U = 1436.0Å3, Z = 2, 4399 observed reflections [F > 4.0σ(F)], R = 4.6%, and wR = 5.7%. Complex 4 crystallizes in the monoclinic space group P21 with a = 11.151(3) Å, b = 18.468(5) Å, c = 17.780(3) Å, β = 92.11(2)°, U=3659.2(15) Å3), Z = 4, 9657 observed reflections [F > 4.0σ(F)], [itR = 2.62%, and wR = 2.61%. Both complexes show a square-planar coordination around the gold atom with chloride trans to aryl. The ketonyl group is unambiguously bonded through the carbon atom in complex 4, but may be disordered in complex 3.