文摘
The reaction of [Fe4C(CO)12{Cu(MeCN)}2] (1) with 3 equivalents of L–L (phen or Me2phen) affords [Cu(L–L)2][Fe4C(CO)12{Cu(L–L)}] (L–L = phen, 2; Me2phen, 3) in good yields. These are protonated by strong acids resulting in [HFe4C(CO)12{Cu(L–L)}] (L–L = phen, 4; Me2phen, 5). The reaction may be reversed with bases, resulting in the quaternary ammonium salts [NR4][Fe4C(CO)12{Cu(phen)}] (6). 4 and 5 react with a slight excess of L–L resulting in the elimination of copper in the form of [Cu(L–L)2]+ and formation of the previously reported [HFe4C(CO)12]− homometallic cluster. Conversely, the reaction of 1 with a monodentate N-ligand such as quinoline, even if used in large excess, results in the substitution product [Fe4C(CO)12{Cu(quinoline)}2] (8), which is then transformed into [Cu(Me2phen)2] [Fe4C(CO)12{Cu(quinoline)}] (9) after reaction with Me2phen. By using the anionic cluster [Fe5C(CO)14{Cu(MeCN)}]− instead of the neutral 1, only substitution has been observed by using both phen and quinoline, resulting in [Fe5C(CO)14{Cu(phen)}]− (10) and [Fe5C(CO)14{Cu(quinoline)}]− (11), respectively. Finally, the reaction of 1 with [Ru(tpy)(bpy)(N4C-C6H4-CN)]Cl affords crystals of [Fe4C(CO)12Cu2Cl{Ru(tpy)(bpy)(N4C-C6H4-CN)}] (12). All compounds 2-12 have been characterized by a combination of spectroscopic (IR, NMR) and crystallographic methods. All these clusters may be viewed as composed by a butterfly [Fe4C(CO)12]2− core bonded to Cu(I) fragments and/or H+ ions.