Short‐Lived Orthobenzyne Complexes with Early Transition Metals of Group IV. First Direct Characterization and Electronic Cartography by Coupling FVT/UV‐PES with Calculations. Issue 23 (11th June 2018)

• Record Type: Journal Article
• Authors: Miqueu, Karinne; Labat, Stéphane; Daiann Sosa Carrizo, E.; Sotiropoulos, Jean‐Marc
• Is Part Of: European journal of inorganic chemistry. Issue 23(2018)
• Page Start: 2717
• Page End: 2729
• Publication Date: 2018-06-11
• Subjects: Photoelectron spectroscopy -- Short‐lived species -- Orthobenzyne complexes -- Transition metals -- Density functional calculations; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201800458
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract : Short‐lived η 2 ‐benzyne metallocene complexes [Cp2 M(η 2 ‐ c ‐C6 H4 )] with group IV metals are important intermediates in organic chemistry, their olefin insertion products being building blocks for aromatic and heterocyclic compounds. For the first time, an electronic cartography of these short‐lived species has been obtained through the determination of their ionization potentials. They have been directly characterized in the gas phase by UV photoelectron spectroscopy, by monitoring, in situ, the thermal β‐H abstraction of benzene from Cp2 MPh2 . The metal impacts the energetic position of the σMC orbitals more strongly than the πCC benzyne orbital (HOMO). This study has been supported by DFT calculations and by NBO, AIM, ELF, CDA, and EDA analyses. The electronic structure of the transient Cp2 Ti(η 2 ‐ c ‐C6 H4 ) complex is peculiar and slightly differs from that of the analogous zirconium and hafnium complexes. The electronic structure is a combination of a metallacyclic and a π complex, whereas with Hf and Zr, the metallacyclic structure appears to be more representative. Abstract : Electronic cartography of short‐lived η 2 ‐benzyne metallocene complexes Cp2 M(η 2 ‐ c ‐C6 H4 ) with group IV metals have been obtained for the first time by coupling flash vacuum thermolysis and UV photoelectron spectroscopy with DFT calculations.