Moussa Mehdi Elsayed, Fleischmann Martin, Balázs Gábor, Virovets Alexander V, Peresypkina Eugenia, Shelyganov Pavel A, Seidl Michael, Reichl Stephan, Scheer Manfred
Institut für Anorganische Chemie, Universität Regensburg, 93040, Regensburg, Germany.
Chemistry. 2021 Jul 7;27(38):9742-9747. doi: 10.1002/chem.202101096. Epub 2021 Jun 1.
The reactions of the cyclo-As complex [Cp*Fe(η -As )] (B) with the Ag and Cu salts of the weakly coordinating anion (WCA) [FAl{OC F (C F )} ] ([FAl] ) are studied. These reactions allow the synthesis of the mononuclear complexes [M(η : η -B) ][FAl] (M=Ag (1), Cu (2)) when a ratio of B/M(FAl) 2 : 1 is used. Compound 1 shows an unusual disorder of the central Ag cation between two π-coordinating cyclo-As ligands, which is absent in 2 pointing to a weak interaction of the Ag center towards the cyclo-As ligands in B. When the ratio of B/Ag(FAl) is changed to 3 : 1 or 1 : 1, the respective coordination compounds [Ag(η -B) ][FAl] (3) and [Ag (η : η -B) ][FAl] (4) are accessible. The coordination modes of the cyclo-As units in 1, 3 and 4 are all different, reflecting the adaptive coordination behavior of B towards Ag ions. The optimized geometries in the gas phase of 1-4 are determined by DFT calculations to support the bonding situation observed in their solid-state structures.
研究了环戊二烯基铁配合物[Cp*Fe(η-As)]（B）与弱配位阴离子（WCA）[FAl{OCF(CF)}]（[FAl]）的银盐和铜盐的反应。当使用B/M(FAl)为2:1的比例时，这些反应可以合成单核配合物[M(η:η-B)][FAl]（M = Ag（1），Cu（2））。化合物1显示出中心银阳离子在两个π配位的环戊二烯基砷配体之间存在不寻常的无序，而在2中不存在这种情况，这表明银中心与B中环戊二烯基砷配体之间存在弱相互作用。当B/Ag(FAl)的比例变为3:1或1:1时，可以得到相应的配位化合物[Ag(η-B)][FAl]（3）和[Ag(η:η-B)][FAl]（4）。1、3和4中环戊二烯基砷单元的配位模式都不同，反映了B对银离子的适应性配位行为。通过DFT计算确定了1-4在气相中的优化几何结构，以支持在其固态结构中观察到的键合情况。
