Work

Pyridylalkenolato-Stabilized Heavier Tetrylenes: Air-Stability Studies and Preliminary Coordination Chemistry

Year: 2026

Type: article

Abstract: High Resolution Image Download MS PowerPoint Slide The potential of 3,3,3-trifluoro-1-(2-pyridyl)prop-1-en-2-ol (tfppOH) as a precursor to synthesize air-stable heavier tetrylenes (HTs), either free or coordinated, was examined. Thus, the stability toward air and water of the homoleptic HTs E(tfppO) 2 (E = Ge ( 1 Ge ), Sn ( 1 Sn )), which were previously reported by Mathur and coworkers and claimed to be highly air-stable, was evaluated together with that of the novel heteroleptic chloro-HTs E(tfppO)Cl (E = Ge ( 2 Ge ), Sn ( 2 Sn )). These analyses have shown that all these compounds are susceptible to undergo hydrolysis at room temperature, albeit at very different rates for each HT. DFT calculations have been used to study the mechanism of these hydrolytic processes. Additionally, a preliminary study of the coordination chemistry of these HTs was conducted. The reactions of 0.5 equiv of [Ir 2 Cl 2 (μ-Cl) 2 (η 5 -Cp*) 2 ] with 2 Ge cleanly afforded the Ge–Ir complex [IrCl 2 (η 5 -Cp*){κ 1 Ge -Ge(tfppO)Cl}] ( 3 Ge ); however, the analogous stannylene 2 Sn led to a complex mixture, and the homoleptic derivatives 1 E resulted in ligand degradation (formation of the HT-free complex [IrCl(η 5 -Cp*){κ 2 N,O -(tfppO)}] ( 4 )). The Ge–Au complexes [AuCl{κ 1 Ge -Ge(tfppO) 2 }] ( 5 Ge ) and [AuCl{κ 1 Ge -Ge(tfppO) 2 } 2 ] ( 6 Ge ) could be prepared by reacting 1 Ge with [AuCl(tht)] (tht = tetrahydrothiophene); however, only the precipitation of dark-purple solids was observed using 1 Sn . On the other hand, both 1 E were capable of rendering the diHT-Ag analogous compounds [Ag{κ 1 E -E(tfppO) 2 } 2 ]OTf (E = Ge ( 7 Ge ), Sn ( 7 Sn )) in their reactions with AgOTf. The air-stability of all these complexes in solution was proven to be similar or lower (for 7 Sn ) than that of the corresponding metal-free HTs.

Source: Inorganic Chemistry

DOI: 10.1021/acs.inorgchem.5c05924

Authors: Sergio García-Vega, Enrique Pérez-Carreño, Javier A. Cabeza, Pablo García-Álvarez

Institutions: Universidad de Oviedo, ORFEO-CINQA Research Network

Language: English

Topic: Synthesis and characterization of novel inorganic/organometallic compounds

Subfield: Inorganic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funder: Agencia Estatal de Investigación