TY - JOUR
T1 - A Copper(II) tris-imidazolylphosphine complex as a functional model of flavonol 2,4-dioxygenase
AU - Lynch, Will E.
AU - Gajdosik-Nivens, Delana
AU - Quilian, Brandon
AU - Padgett, Clifford W.
AU - Peek, Nathan
AU - Petrillo, Anthony
AU - Stone, John W.
N1 - Publisher Copyright:
© 2019 Elsevier B.V.
PY - 2019/6/5
Y1 - 2019/6/5
N2 - Reaction of tetrakis(acetonitrile)copper(I) perchlorate ([Cu(NCCH 3 ) 4 ][ClO 4 ]), tris-1-ethyl-4-methylimidazolylphosphine (T1Et4MeIP) (1) and 3-hydroxyflavone (flavH) under ambient conditions produces an in-situ generated flavonol bound copper(II) complex, which converts to a stable green complex that formulates to [Cu(T1Et4MeIP)(flav)][ClO 4 ] (2). The crystal structure of 2 was determined by X-ray diffraction and crystallizes in a triclinic system (P1¯) with unit cell dimensions of a = 14.537(15) Å, b = 15.794(14) Å, c = 17.044(17) Å, α = 65.58(3)˚, β = 86.80(5)˚, γ = 73.34(4)˚, V = 3376(6) Å 3 and Z = 2. While the five-coordinate copper(II) complex is stable under ambient conditions in the solid state, it undergoes oxidative scission of the flavonol pyrone ring under photolytic (300 nm) and/or thermal (120 °C) conditions in the presence of molecular oxygen. The degradative process produces the corresponding methylated products: methylbenzoate, methyl salicylate and N,N-dimethylbenzamide. In addition, the previously undisclosed single crystal X-ray structure of tris-1-ethyl-4-methylimidazolylphosphine (1), T1Et4MeIP, is also reported.
AB - Reaction of tetrakis(acetonitrile)copper(I) perchlorate ([Cu(NCCH 3 ) 4 ][ClO 4 ]), tris-1-ethyl-4-methylimidazolylphosphine (T1Et4MeIP) (1) and 3-hydroxyflavone (flavH) under ambient conditions produces an in-situ generated flavonol bound copper(II) complex, which converts to a stable green complex that formulates to [Cu(T1Et4MeIP)(flav)][ClO 4 ] (2). The crystal structure of 2 was determined by X-ray diffraction and crystallizes in a triclinic system (P1¯) with unit cell dimensions of a = 14.537(15) Å, b = 15.794(14) Å, c = 17.044(17) Å, α = 65.58(3)˚, β = 86.80(5)˚, γ = 73.34(4)˚, V = 3376(6) Å 3 and Z = 2. While the five-coordinate copper(II) complex is stable under ambient conditions in the solid state, it undergoes oxidative scission of the flavonol pyrone ring under photolytic (300 nm) and/or thermal (120 °C) conditions in the presence of molecular oxygen. The degradative process produces the corresponding methylated products: methylbenzoate, methyl salicylate and N,N-dimethylbenzamide. In addition, the previously undisclosed single crystal X-ray structure of tris-1-ethyl-4-methylimidazolylphosphine (1), T1Et4MeIP, is also reported.
KW - 3-Hydroxyflavone
KW - Copper complex
KW - Dioxygenase
KW - X-ray structure
UR - http://www.scopus.com/inward/record.url?scp=85062301893&partnerID=8YFLogxK
U2 - 10.1016/j.molstruc.2019.02.078
DO - 10.1016/j.molstruc.2019.02.078
M3 - Article
SN - 0022-2860
VL - 1185
SP - 99
EP - 106
JO - Journal of Molecular Structure
JF - Journal of Molecular Structure
ER -