Cyclic Bis‐alkylidene Complexes of Titanium and Zirconium: Synthesis, Characterization, and Reaction

Abstract

DedicatedtoProf. Pierre H. Dixneuf for his great contribution to the good friendship between the Chinese and French chemistry communities.

Dinitrogen activation by a titanium hydride complex supported by 2-butene ligand

“…Cyclic bis-alkylidene titanium complex 1 was synthesized according to the published procedures. 10 Other commercially available reagents were used without purification.…”

“…9 As an extension of our work, we continue to expand this field to prepare the corresponding titanium hydrides and explore their reactivities with N 2 gas. In this work, by hydrogenating titanacyclopentatriene complex 1 , 10 stemming from the 1,4-dilithio-1,3-butadiene precursor, we obtained Ti-hydride complex 2 , {[(2-butene)(C 5 H 5 )Ti](μ-H) 2 Li(THF) 3 }. The subsequent reaction of 2 with dinitrogen led to the formation of Ti-N 2 complexes 4 and 5 , {[((2-butene)(C 5 H 5 )Ti) 2 (μ 2 -η 1 ,η 1 -N 2 )][Li(THF) 4 ]} and {[(2-butene)(C 5 H 5 )Ti] 2 (μ 2 -η 1 ,η 1 -N 2 )}, respectively.…”

C,C- and C,N-Chelated Organocopper Compounds

“…Although neutral N,N-chelated spiro copper complexes are relatively common, the anionic C,N- or C,C-cheated spiro counterparts are sporadic. As mentioned above, Xi’s group found that the C,C-bidentate ligand is an excellent platform to build up diversified coordination complexes across the periodic table [ 32 , 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 ]. The chelating effect increases the thermal stability of these organometallic species, facilitating isolation and following characterization.…”