Synthesis, Structures and Electrochemistry of New Carbonylnickel Octacarbide Clusters: The Distorting Action of Carbide Atoms in the Growth of Ni Cages and the First Example of the Inclusion of a Carbon Atom within a (Distorted) Ni Octahedral Cage

摘要: The reaction of [Ni 10 C 2 (CO) 15 ] 2- in thf with a large excess CdCl ·2.5H O (8-15 equiv.) resulted the formation new carbonyl octacarbide clusters [H 5-n Ni 36 8 -(Cd Cl 3 )] n- (n = 3-5), which undergo partial CO replacement to give 36-y 34-y (MeCN) (Cd 3- (y 0-2) after prolonged time MeCN. Treatment former an NaOH afforded larger 7-n 42+y 44+y -(CdCl)] 6, 7 ; y 0, 1) octacarbides. Their structures (as well as those analogous Br-containing clusters) have been fully elucidated by single-crystal X-ray analysis their [Me 4 N] 5 )]·(7-2y)MeCN·yC 6 H 14 0.40), )]·5MeCN 0.61), (CdCl)]·(5-y)MeCN 0.19) and [HNi (CdBr)]·(6-y)MeCN salts, feature highly distorted metal cages (due inclusion several carbide atoms), presence partially vacant capping Ni(CO) fragments. This aspect, together fact that all these species protonation-deprotonation equilibria solution reversible redox processes under electrochemical control, indicates detailed description molecular containing few dozen atoms might be sometimes rather troublesome non-trivial. A complete elucidation systems can achieved only combining structural, chemical, spectroscopic, spectroelectrochemical studies.