Synthesis and structural systematics of mixed triphenylphosphine/imidazole base adducts of silver(I) oxyanion salts †
作者:Augusto Cingolani、Effendy、Fabio Marchetti、Claudio Pettinari、Brian W. Skelton、Allan H. White
DOI:10.1039/a906624a
日期:——
From the interaction between imidazole-type ligands B and [Ag(PPh3)4]X (X = NO3, BF4, ClO4 or CF3CO2), [Ag(PCy3)2(NO3)] and [Ag(PPh3)X)] (X = NO2 or CH3SO3), new ionic mononuclear [Ag(PR3)4ân(B)n]+[X]â (R = Ph or Cy) and neutral mono- ([Ag(PR3)3ân(B)n(X)]) and di-nuclear ([Ag(PPh3)(B)(µ-X)}2]) complexes have been obtained which have been characterized through elemental analysis, IR and far-IR, conductivity, 1H NMR and in some cases also by vaporimetric molecular weight measurements and 31P NMR. Stoichiometries and molecular structures are dependent on the nature of the azole (steric hindrance and basicity), of the counter ion, and on the number of the P-donor ligands in the starting reactants. Solution data are consistent with a partial dissociation of complexes, occurring through breaking of both AgâN and AgâP bonds. The majority of the possible Ph3P/imidazole base combinations have been characterized structurally by room-temperature single crystal X-ray studies, thus: [Ag(PPh3)3(4-Ph-im)]NO3 (4-Ph-im = 4-phenylimidazole), [Ag(PPh3)2B2]NO3 for B = imidazole (Him) or 2-methyl-imidazole (2-Me-im), [Ag(PPh3)(2-Me-im)3][CF3CO2], [Ag(PPh3)2(2-Me-im)(O2NO)], [Ag(PPh3)(1-Me-im)(µ-OSOCH3O)}2] and [Ag(PPh3)(Him)(µ-ONO)}2]; the latter is a mixture of isomers in which one or both oxygen atoms of the anions interact with silver atoms. In the methanesulfonate complex the interactions of the anions with the silver may be regarded as a perturbation on a proto-linear PâAgâN array (AgâP,N 2.3662(6), 2.189(1) Ã
; PâAgâN 144.28(6)°).
来自咪唑型配体 B 和 [Ag(PPh3)4]X(X=NO3、BF4、ClO4 或 CF3CO2)、[Ag(PCy3)2(NO3)] 和 [Ag(PPh3)X)] 之间的相互作用(X=NO2 或 CH3SO3)、新离子单核 [Ag(PR3)4−n(B)n]+[X]−(R=Ph 或 Cy)和中性单核 ([Ag(PR3) )3→n(B)n(X)]) 和双核 ([Ag(PPh3)(B)(µ-X)}2]) 配合物已获得,并通过元素分析、红外光谱进行了表征以及远红外、电导率、1H NMR,在某些情况下还通过蒸气分子量测量和 31P NMR。化学计量和分子结构取决于唑的性质(空间位阻和碱性)、抗衡离子的性质以及起始反应物中P-供体配体的数量。溶液数据与复合物的部分解离一致,这是通过 Ag-N 和 Ag-P 键的断裂而发生的。大多数可能的 Ph3P/咪唑碱组合已通过室温单晶 X 射线研究进行了结构表征,因此: [Ag(PPh3)3(4-Ph-im)]NO3 (4-Ph-im =) 4-苯基咪唑), [Ag(PPh3)2B2]NO3 for B = 咪唑 (Him) 或 2-甲基咪唑 (2-Me-im), [Ag(PPh3)(2-Me-im)3][ CF3CO2]、[Ag(PPh3)2(2-Me-im)(O2NO)]、[Ag(PPh3)(1-Me-im)(µ-OSOCH3O)}2] 和 [Ag(PPh3)(他)(µ-ONO)}2];后者是异构体的混合物,其中阴离子的一个或两个氧原子与银原子相互作用。在甲磺酸盐配合物中,阴离子与银的相互作用可被视为对原始线性 P−Ag−N 阵列的扰动 (Ag−P,N 2.3662(6), 2.189(1) ×; Pâ Ag-N 144.28(6)°)。