Department of Chemistry, Texas A&M University, College Station, Texas 77843, USA.
Inorg Chem. 2011 May 16;50(10):4238-40. doi: 10.1021/ic200394q. Epub 2011 Apr 14.
The potential for reductive elimination of fluorine from dinuclear gold(II) for catalysis has prompted our efforts to synthesize a dinuclear gold(II) fluoride complex. This has been achieved with bis(2,6-dimethylphenyl)formamidinate bridging ligands. In order to obtain this product, it was necessary first to synthesize the corresponding dinuclear gold(II) nitrate, which reacts readily with KF in a metathesis reaction. The nitrate complex and fluoride complexes have been structurally characterized. The Au-Au distance in the dinuclear fluoride, 2.595 Å, is longer than the distance found in the analogous chloride complex, 2.567 Å. This result is consistent with the presence of a fluoride "π electron effect" on the filled Au 5d orbitals. The Raman spectrum shows an Au-Au stretch at 206 cm(-1), which agrees with Woodruff's rules and the density functional theory computational model used for modeling the complex.
双(2,6-二甲基苯基)甲脒桥联配体促使我们努力合成双核金(II)氟化物配合物，以探索其用于催化时还原消除氟的可能性。为了获得该产物，首先需要合成相应的双核金(II)硝酸盐，后者可与 KF 发生转位反应而轻易得到。对硝酸盐复合物和氟化物复合物进行了结构表征。双核氟化物中 Au-Au 距离为 2.595 Å，长于类似的氯化物复合物中 Au-Au 距离 2.567 Å。这一结果与氟化物对充满的 Au 5d 轨道的“π电子效应”有关。拉曼光谱在 206 cm(-1)处显示 Au-Au 伸缩振动，这与 Woodruff 规则和用于模拟该配合物的密度泛函理论计算模型一致。
