Ball P J, Shtoyko Tanya Rarog, Krause Bauer Jeanette A, Oldham Warren J, Connick William B
Department of Chemistry, University of Cincinnati, PO Box 210172, Cincinnati, Ohio 45221-0172, USA.
Inorg Chem. 2004 Jan 26;43(2):622-32. doi: 10.1021/ic0348648.
Two pseudo-para substituted bis-diimino[2.2]paracyclophane ligands (4,16-bis(picolinaldimine)-[2.2]paracyclophane (BPPc) and 4,16-bis(methyl-picolinaldimine)-[2.2]paracyclophane (BmPPc)) were prepared by the condensation reaction of the appropriate picolinaldimine with 4,16-diamino-[2.2]paracyclophane (2). An improved synthesis of 2 from [2.2]paracyclophane also is reported. BPPc (3a): monoclinic, P2(1)/c, a = 8.2238(11) A, b = 15.336(2) A, c = 8.4532(11) A, beta = 98.578(3) degrees, V = 1054.2(2) A(3), Z = 2. To investigate the binding properties of the bis-diimino[2.2]paracyclophane ligands, binuclear rhenium(I) tricarbonyl chloride complexes Re(CO)(3)Cl(micro-BPPc) (5a) and Re(CO)(3)Cl(micro-BmPPc) (5b) were prepared and fully characterized by infrared spectroscopy, (1)H NMR spectroscopy, elemental analysis, UV-visible absorption spectroscopy, and cyclic voltammetry. Two model complexes, Re(tolyl-pyCa)(CO)(3)Cl (4) (tolyl-pyCa = N-(p-tolyl)-2-pyridinecarboxaldimine) and Re(CO)(3)Cl(micro-PBP) (6) (PBP = p-phenylenebis(picolinaldimine)), also are reported. The dimeric compounds 5 and 6 each undergo two one-electron, predominantly diimine-centered reduction processes. Spectroscopic data and comproportionation constants (5a, 23 +/- 9; 5b, 23 +/- 9; 6, 2750 +/- 540) are consistent with relatively weak interactions between the diimine groups mediated by the paracyclophane bridging group, and these results are consistent with steric and electronic factors.
通过适当的吡啶甲亚胺与4,16 - 二氨基 - [2.2]对环芳烷（2）的缩合反应制备了两种伪对位取代的双二亚氨基[2.2]对环芳烷配体（4,16 - 双（吡啶甲亚胺基） - [2.2]对环芳烷（BPPc）和4,16 - 双（甲基 - 吡啶甲亚胺基） - [2.2]对环芳烷（BmPPc））。还报道了一种从[2.2]对环芳烷改进合成2的方法。BPPc（3a）：单斜晶系，P2(1)/c，a = 8.2238(11) Å，b = 15.336(2) Å，c = 8.4532(11) Å，β = 98.578(3)°，V = 1054.2(2) ų，Z = 2。为了研究双二亚氨基[2.2]对环芳烷配体的结合性质，制备了双核铼（I）三羰基氯配合物[Re(CO)₃Cl]₂(μ - BPPc)（5a）和[Re(CO)₃Cl]₂(μ - BmPPc)（5b），并通过红外光谱、¹H NMR光谱、元素分析、紫外 - 可见吸收光谱和循环伏安法进行了全面表征。还报道了两种模型配合物，Re(甲苯基 - pyCa)(CO)₃Cl（4）（甲苯基 - pyCa = N - （对甲苯基） - 2 - 吡啶甲亚胺）和[Re(CO)₃Cl]₂(μ - PBP)（6）（PBP = 对亚苯基双（吡啶甲亚胺））。二聚体化合物5和6各自经历两个单电子、主要以二亚胺为中心的还原过程。光谱数据和归中常数（5a，23 ± 9；5b，23 ± 9；6，2750 ± 540）与由对环芳烷桥连基团介导的二亚胺基团之间相对较弱的相互作用一致，并且这些结果与空间和电子因素一致。
