Canadian Journal of Chemistry p. 2201 - 2208 (1996)
Update date:2022-08-12
Topics:
Aquino, Manuel A.S.
White, Christopher A.
Bensimon, Corinne
Greedan
Crutchley, Robert J.
The novel ligand 4,4′-dicyanamidobiphenyl dianion (bp2-) has been synthesized and characterized by 13C NMR spectroscopy, cyclic voltammetry, and crystallography. The crystal structure of [Ph4As]2[bp]·H2O showed that bp2- is approximately planar with a dihedral angle of 8.2° between phenyl ring planes and the cyanamide groups in an ami conformation. The water of crystallization is asymmetrically hydrogen bonded between cyanamide groups of adjacent bp2- ions. The crystal data for C62H48N4As2+H2O are monoclinic crystal system and space group P21/c with a = 12.998(5) A?, b = 13.465(4) A?, c = 28.703(13) A?, β = 98.94(3)°, V = 4963(3) A?3, and Z = 4. The structure was refined by using 4555 reflections with I > 2.5σ(I) to an R factor of 0.058. The complex, [{(NH3}5Ru}2(μ-bp)][X]4, where X = tosylate or PF6- ions, was also synthesized and characterized by 1H NMR spectroscopy, cyclic voltammetry, spectroelectrochemistry, and temperature-dependent magnetic susceptibility measurements. From cyclic voltammetry measurements, the comproportionation constants to form the mixed-valence complex [{(NH3}5Ru)2(μ-bp)]3+ were estimated to be 4.1, 16, and 22 in water, acetonitrile, and nitromethane, respectively. The trend and magnitude of Kc suggests solvent valence trapping of a weakly coupled Class II ion. The MMCT band of the mixed-valence complex had to be deconvoluted from the low-energy LMCT band and had the following properties in acetonitrile, νmax = 8400 cm-1, εmax = 3300 M-1 cm-1, and Δν1/2 = 3300 cm-1. The weak superexchange mediating properties of bp2- compared to 1,4-dicyanamidobenzene dianion were suggested to arise from the larger barrier to the formation of the radical anion bp-.
View More
Taizhou Elitechemie MediPharma Technology Co.,Ltd.
Contact:+86-523-86810021
Address:Building G14,NO.1 Avenue,China Medical City, Taizhou, Jiangsu,China
Wuxi Innopal International Trade CO.,LTD
Contact:+86-510-80711901-8003
Address:Room 402,Building 5,Longze Garden,No.17,South huanjiu Road,Yixing City, Jiangsu,China
Shanghai Sunwise Chemical Co., Ltd
website:http://www.sunwisechem.com
Contact:86-021-33883180
Address:Room 10E, Building G, Westlink Center, No. 2337 Gudai Road, Minhang District, Shanghai, China PC: 201100
Contact:86-10-62664360
Address:Building 10,No.18 AnNingZhuang East Road, GuangHua Pioneer Park,HaiDian District, BeiJing China
Shaanxi HuaTai Bio-fine chemical company Ltd
Contact:86-029-87862197
Address:No. 5, 3rd Floor, 29 Yanta North Road, Beilin Dist.
Doi:10.1021/ic800024n
(2008)Doi:10.1016/j.ijms.2010.07.024
(2011)Doi:10.1002/zaac.19703720210
(1969)Doi:10.1002/anie.201705641
(2017)Doi:10.1021/ja508265b
(2014)Doi:10.1016/0031-9422(89)85043-5
(1989)
