Fedushkin Igor L, Khvoinova Natalie M, Baurin Andrey Yu, Fukin Georgii K, Cherkasov Vladimir K, Bubnov Mikhail P
G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Tropinina 49, 603950 Nizhny Novgorod, GSP-445, Russia.
Inorg Chem. 2004 Nov 29;43(24):7807-15. doi: 10.1021/ic048801g.
The germanium(II) compound (dpp-BIAN)GeCl (1), which contains the radical anion of dpp-BIAN can be prepared either by reacting free dpp-BIAN ligand with 2 equiv of GeCl2(1,4-dioxane) in Et2O or by metathetical reaction of the sodium salt of dpp-BIAN with germanium dichloride in Et2O or benzene. The reaction of benzene solutions of 1 with 2 or 3 equiv of HCl led to protonation of the dpp-BIAN ligand affording [(dpp-BIAN)(H)2]+[GeCl3]- (2) and [[(dpp-BIAN)(H)2+]2(Cl-)]+ [GeCl3]- (3), which incorporate the radical cation of the protonated ligand. Compounds 1-3 have been characterized by elemental analysis, IR, UV-vis, and electron spin resonance (ESR) spectroscopy. Molecular structures of 1-3 were determined by single-crystal X-ray diffraction. In molecule 1, the Ge atom is positioned at the apex of the slightly distorted trigonal pyramid. The Ge-N bond lengths in 1 are 2.0058(19) and 2.004(2) A. The molecular structure of 2 consists of contact ions [(dpp-BIAN)(H)2]+ and [GeCl3]-. In the molecular structure of 3, two radical cations of [(dpp-BIAN)(H)2]+ are "coordinated" by the chlorine anion. The ESR signal of 1 indicates the presence of a dpp-BIAN radical anion and shows a hyperfine structure due to the coupling of an unpaired electron to 14N, 73Ge, 35Cl, 37Cl, and 1H nuclei (AN=0.48 (2 N), AGe=0.96, ACl=0.78 (35Cl), ACl=0.65 (37Cl), AH=0.11 (4 H) mT, g=2.0014). Both 2 and 3 reveal ESR signals of radical cation [(dpp-BIAN)(H)2]*+ (septet, AN=0.53, AH=0.48 mT, g=2.0031).
含有dpp - BIAN自由基阴离子的锗（II）化合物(dpp - BIAN)GeCl（1），可以通过使游离的dpp - BIAN配体与2当量的GeCl₂(1,4 - 二氧六环)在乙醚中反应，或者通过dpp - BIAN的钠盐与二氯化锗在乙醚或苯中进行复分解反应来制备。1的苯溶液与2或3当量的HCl反应导致dpp - BIAN配体质子化，得到[(dpp - BIAN)(H)₂]⁺[GeCl₃]⁻（2）和[[(dpp - BIAN)(H)₂⁺]₂(Cl⁻)]⁺ [GeCl₃]⁻（3），它们包含质子化配体的自由基阳离子。化合物1 - 3已通过元素分析、红外光谱、紫外 - 可见光谱和电子自旋共振（ESR）光谱进行了表征。1 - 3的分子结构通过单晶X射线衍射确定。在分子1中，Ge原子位于略微扭曲的三角锥的顶点。1中的Ge - N键长为2.0058(19)和2.004(2) Å。2的分子结构由接触离子[(dpp - BIAN)(H)₂]⁺和[GeCl₃]⁻组成。在3的分子结构中，两个[(dpp - BIAN)(H)₂]⁺自由基阳离子由氯阴离子“配位”。1的ESR信号表明存在dpp - BIAN自由基阴离子，并由于未成对电子与¹⁴N、⁷³Ge、³⁵Cl、³⁷Cl和¹H核的耦合而显示出超精细结构（AN = 0.48 (2 N)，AGe = 0.96，ACl = 0.78 (³⁵Cl)，ACl = 0.65 (³⁷Cl)，AH = 0.11 (4 H) mT，g = 2.0014）。2和3都显示出自由基阳离子[(dpp - BIAN)(H)₂]⁺的ESR信号（七重峰，AN = 0.53，AH = 0.48 mT，g = 2.0031）。
