409306-04-3Relevant academic research and scientific papers
First structurally characterized silver(I) derivatives with nonfluorinated β-diketones
Cingolani, Augusto,Effendy,Marchetti, Fabio,Pettinari, Claudio,Pettinari, Riccardo,Skelton, Brian W.,White, Allan H.
, p. 1151 - 1161 (2002)
Synthetic, spectroscopic, and single-crystal X-ray structural studies of diverse complexes of silver(I) acylpyrazolonate salts AgQR′ (QH = 1-phenyl-3-methyl-4-R′(C = O)-pyrazol-5-one; Q1, R = Ph; Q2, R′ = CF3; Q3, R′ = Me) with neutral ligands L = unidentate PR3 (R = Ph, o-tolyl, cyclohexyl) and Hmimt (1-methyl-2-mercaptoimidazole) and bidentate dppe (Ph2P(CH2)2PPh2) and trimen (N,N,N′-trimethylethylenediamine) define the donor capability of the anionic QR′ ligand in a variety of roles. In the free ligand Q3H (which crystallizes in the monoclinic space group C2/c (no. 15), Z = 8, unit cell parameters a = 17.981(6) A, b = 5.0641(4) A, c = 24.271(6) A, and β = 99.67-(2)°), the acidic OH group hydrogen-bonds intramolecularly to the adjacent pyrazolone oxygen, i.e., the two oxygen atoms are cis, true of the other QR′ species structurally characterized here in their anionic complexed forms, in which they chelate the silver in the usual β-diketonate manner, but not of the free anion, found in the array [Ag(Ph3P)(Hmimt)2](Q1) (triclinic space group P1 (no. 2), Z = 2, unit cell parameters a = 11.553(1) A, b = 11.943-(1) A, c = 15.479(2) A, α = 74.829(2)°, β = 76.094(2)°, and γ = 78.185(2)°), or [Ag(trimen)Q1] (monoclinic space group P21/c (no. 14), Z = 4, unit cell parameters a = 7.982(1) A, b = 12.299(2) A, c = 21.507(3) A, and β = 95.119(3)°), which forms an infinite one-dimensional polymer string, Q1 linking successive silver(I) atoms by coordination by way of the unsubstituted nitrogen and the pyrazolonate oxygen. In all [Ag(R3P)2(chelate-Q1)] (R =Ph, Cy) complexes, P2Ag(O,O′) arrays are found (R = Ph, monoclinic space group C2/c (no. 15), Z = 8, unit cell parameters a = 16.193(8) A, b = 13.859(7) A, c = 39.306(7) A, and β = 100.02(3)°; R = Cy, triclinic space group P1 (no. 2), Z = 2, unit cell parameters a = 10.4655(9) A, b = 12.079(1) A, c = 22.804(2) A, α= 104.872(2)°, δ = 95.180(2)°, and γ = 104.144(2)°), also true of [Ag(Ph3P)2(O,O′-Q2)] (triclinic space group P1 (no. 2), Z = 2, unit cell parameters a = 10.672(2) A, b = 10.710(2) A, c = 18.713(3) A, α = 87.573(2)°, β = 80.972(2)°, and γ = 81.734(2)°), whereas [Ag(o-tol3P)Q1] (monoclinic space group P21/c (no. 14), Z = 2 dimers, unit cell parameters a = 11.8221(6) A, b = 13.2601(6) A, c = 20.5141(10) A, and β = 91.758(1)°) exists as a dinuclear species containing two AgO2NP units where the acylpyrazolonate is coordinated in a bridging O,O′-Q-N fashion. Silver atoms are four-coordinate in all except the Hmimt complex.
