Ruspic Christian, Harder Sjoerd
Anorganische Chemie, Universität Duisburg-Essen, Universitätsstrasse 5-7, 45117 Essen, Germany.
Inorg Chem. 2007 Nov 26;46(24):10426-33. doi: 10.1021/ic701479r. Epub 2007 Oct 31.
Reaction of (DIPP-nacnac)CaN(SiMe3)2.THF (DIPP-nacnac=CH{(CMe)(2,6-iPr2C6H3N)}2) with NH3 gave the heteroleptic complex (DIPP-nacnac)CaNH2.(NH3)2 which crystallized as a dimer with bridging NH2- ions. In contrast to other heteroleptic (DIPP-nacnac)calcium amides, (DIPP-nacnac)CaNH2.(NH3)2 is remarkably stable toward ligand exchange. Reaction of (DIPP-nacnac)CaH.THF with Me3SiCN gave the heteroleptic complex (DIPP-nacnac)CaCN.THF that crystallized as a trimer. The CN- ions bridge in a linear fashion between the Ca2+ ions. In a new synthetic route (DIPP-nacnac)CaN(SiMe3)2.THF reacted with Et3NH+Cl- to give (DIPP-nacnac)CaCl.THF, which crystallized as a dimer with bridging Cl- ions. The exceptional stability of these aggregates toward ligand-exchange reactions, which would give insoluble homoleptic Ca(NH2)2, Ca(CN)2, or CaCl2, is remarkable and likely due to their multinuclear nature.
（DIPP - nacnac）CaN(SiMe₃)₂·THF（DIPP - nacnac = CH{(CMe)(2,6 - iPr₂C₆H₃N)}₂）与NH₃反应生成杂配配合物（DIPP - nacnac）CaNH₂·(NH₃)₂，其以具有桥连NH₂⁻离子的二聚体形式结晶。与其他杂配（DIPP - nacnac）钙酰胺不同，（DIPP - nacnac）CaNH₂·(NH₃)₂对配体交换具有显著的稳定性。（DIPP - nacnac）CaH·THF与Me₃SiCN反应生成杂配配合物（DIPP - nacnac）CaCN·THF，其以三聚体形式结晶。CN⁻离子以线性方式在Ca²⁺离子之间桥连。在一条新的合成路线中，（DIPP - nacnac）CaN(SiMe₃)₂·THF与Et₃NH⁺Cl⁻反应生成（DIPP - nacnac）CaCl·THF，其以具有桥连Cl⁻离子的二聚体形式结晶。这些聚集体对配体交换反应具有非凡的稳定性，配体交换反应会生成不溶性的同配Ca(NH₂)₂、Ca(CN)₂或CaCl₂，这很显著，可能是由于它们的多核性质。
