WCA-Cluster: Synthesis and characterization of polyatomic elemental clusters of groups 15 to 18 and their simple metal complexes as salts of weakly coordinating anions

延长期间的WCA-簇项目的目标是在第一个资助期的相关结果的基础上，合成和表征具有教科书性质的反应性阳离子[RC]+，作为极弱配位的阴离子[WCA]-的盐。为了使这些物质部分从凝聚相中的质谱学已知离子中稳定下来，人们需要优良的阴离子[WCA]-。在第一个资助期，我们开发了一种系统地获取具有非常稳定的阴离子的试剂。这些将在第二个资金期用于从第15-17族元素制备簇状/笼状阳离子，或产生WCA-“裸”金属阳离子盐(M=铜、金、镉、汞、锡、铅)的合成子，并用于同原子或二元笼状或簇状化合物与第15-17族元素的络合。具体的项目目标是迄今未知的阳离子，如[As9]+、[As8]2+、[S5]+、[I9]+或[P3e]+(E=S、Se、Te)，以及具有中性元素或笼状化合物的络合阳离子，即X2、CHn、Ng、CH3E4、CH4E4(X=Cl、BrI；Ng=Kr、Xe；CH=S、Se；n=2-20；E=P、As)。在另一条边线上，直接由第一个供资期产生，还应研究催化可能的--[(P4)FeCp(CO)2]+[Al(ORF)4]中配位的P4与H-SiR3、H-NR2或H-OR等简单亲核试剂的亲核官能化。

The goals for the WCA-Cluster project in the prolongation period aim, building on the relevant results from the first funding period, at synthesis and characterization of Reactive Cations [RC]+ with textbook character as salts of very weakly coordinating anions [WCA]–. To stabilize these partly from mass spectrometry known ions in condensed phases, one needs excellent anions [WCA]–. In the first funding period we have developed a systematic access to reagents with extraordinarily stable anions. Those shall be applied in the second funding period to prepare cluster-/cage-cations from elements of group 15-17, or to yield synthons for WCA-salts of “naked” metal cations (M = Cu, Au, Cd, Hg, Sn, Pb) and to use those for complexation of homoatomic or binary cage- and cluster-compounds with elements from group 15-17. Specific project goals are hitherto unknown cations such as [As9]+, [As8]2+, [S5]+, [I9]+ or [P3E]+ (E = S, Se, Te) as well as complex cations with neutral elements or cage compounds, i.e. X2, Chn, Ng, Ch3E4, Ch4E4 (X = Cl, Br, I; Ng = Kr, Xe; Ch = S, Se; n = 2-20; E = P, As). In a further side line, directly resulting from the first funding period, the – evtl. also catalytically possible – nucleophilic functionalization of the coordinated P4 in [(P4)FeCp(CO)2]+[Al(ORF)4]– with simple nucleophiles like H-SiR3, H-NR2 or H-OR shall be investigated.