ИСТИНА

In 1981, M.E. Volpin initiated research on the development of a method for the synthesis of acetylene complexes of titanocene not containing additional stabilizing ligands. A year later, we developed such general method for the synthesis of acetylene complexes of titanocene and synthesized the first Cp2Ti(RC2R) complexes (1)1 that did not contain additional ligands. Analogous acetylene complexes with various substituents in the Cp-rings and, in particular, the first acetylene complexes of ansa-titanocene derivatives were obtained in a similar way. The developed method was successfully used for the synthesis of various acetylene complexes of zirconocene and its Cp-substituted derivatives. Later, unusual complexes of titanocene and zirconocene with trans-acetylene ligands (2)2, as well as the first hafnium acetylene complexes, were synthesized. Later, when studying the reactions of group IVB metallocenes (generated in various ways) with conjugated di- and polyacetylenes, we first synthesized and structurally characterized stable five-membered metallacyclocumulene complexes Сp2M(η4-RC4R), where M = Ti, Zr, Hf (3)3, and the first organometallic radialens (4). We have shown for the first time that the metallocene particle is able to migrate along the polyacetylene chain. In 2002-2004, the reaction of group IVB metallocenes with reduced 1,4‑dichlorobutine produced the first metallacyclopentine complexes of titanium and zirconium (5)4,5.