The chemistry of titanocene dipnictene and pnictinidene complexes

• Applicant: Dr. Christian Hering-Junghans
• Subject Area: Inorganic Molecular Chemistry - Synthesis and Characterisation
• Term: since 2022
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 516840181

This project aims to utilize aryl-substituted triphosphoranes for the synthesis of phosphorus-containing molecules by exploiting their unique reactivity towards titanocene precursors. Using titanocene complexes of the type Cp2Ti(P2Ar2) (Ar = aryl group) in reactions with a variety of Lewis bases, an enhancement of the reactivity of the P2Ar2-ligand is expected and to give access to unprecedented titanocene η1-diphosphene complexes in a first step. While in the next step these complexes will be converted with N-heterocyclic carbenes to realize push-pull stabilized diphosphenes. The analogous arsenic compounds will be investigated as well. Moreover, in an explorative work package the reactivity towards alkynes, nitriles or isonitriles will be explored to build P-containing heterocycles at Ti, which can then be released through transmetalation reactions, akin to what has been established with related zirconium systems. In another work package the reactivity of the titanocene precursor Cp2Ti(btmsa) (btmsa = C2(SiMe3)2) towards (ArPn)3 (Pn = P, As) in the presence of phosphines, PR3, and phosphine oxides, OPR3, will be studied in detail. These studies are expected to result in the formation of terminal titanocene phosphinidene and arsinidene complexes. The phosphinidene complexes will be used to establish a titana-phospha-Wittig reaction, to access phosphaalkenes with intermediate steric bulk on the phosphaalkene unit.

• DFG Programme: Research Grants