From Neutral Zn<sub>4</sub>O<sub>4</sub> Clusters to a Cationic ZnO Dimer in Solution
作者:Matthias Driess、Klaus Merz、Robert Schoenen
DOI:10.1021/om061108b
日期:2007.4.1
is reported. The formation and fate of the resulting cationic Zn4O4 degradation products by reaction of 1a and 1b with B(C6F5)3 in the presence of different organic donor substrates have been studied by means of ESI mass spectrometry. While 1a affords the cationic monozinc complexes [MeZn(L)]+ (2a: L = THF, 2b: 15-c-5, 2c: DMAP), the cluster 1b furnishes in the presence of DMAP [MeZn(OSiMe3)2Zn(DMAP)2]+
四聚体ZnO聚集体[(i PrO)ZnMe] 4(1a)和[(Me 3 SiO)ZnMe] 4(1b)作为氧化锌催化剂上低配位锌中心和活性位点的分子模型的潜在来源的适用性被报道。通过ESI质谱研究了在不同有机供体底物的存在下1a和1b与B(C 6 F 5)3反应生成的阳离子Zn 4 O 4降解产物的形成和命运。而1a得到的阳离子monozinc配合物[MeZn(L)] +(2A:L = THF,2B:15-C-5,2C:DMAP),群集1B在DMAP的存在下配料[MeZn(OSiMe 3)2 Zn(上DMAP)2 ] +(3),溶液中的第一个二聚ZnO聚集阳离子和[MeB(C 6 F 5)3 ]阴离子。此外,中性双核ZnO聚集体[(Me 3 SiO)Zn(C 6 F 5)thf] 2(4)由Me / C 6 F产生5交换反应作为最终产物,已通过NMR光谱和单晶X射线衍射分析进行了表征。