Publikace detail

Heterocycles Derived from Generating Monovalent Pnictogens within NCN Pincers and Bidentate NC Chelates: Hypervalency versus Bell-Clappers versus Static Aromatics

Rok: 2018

Druh publikace: článek v odborném periodiku

Název zdroje: Organometallics

Název nakladatele: American Chemical Society

Místo vydání: Washington

Strana od-do: 2481-2490

Tituly:

Jazyk	Název	Abstrakt	Klíčová slova
cze	Heterocykly generované z jednomocných pniktogenů	Byla studována možnost tvorby nových heterocyklů generovaných z jednomocných pniktogenů.	Heterocykly; generované; jednomocných; pniktogenů
eng	Heterocycles Derived from Generating Monovalent Pnictogens within NCN Pincers and Bidentate NC Chelates: Hypervalency versus Bell-Clappers versus Static Aromatics	Generating monovalent pnictogens within NCN pincers has resulted in the isolation of three distinct types of 1,2-azaheteroles, highly aromatic nitrogen analogues like pyrazole-based 5, aromatic yet fluxional P- and As-derived bell-clappers 1 and 2, and hypervalent Sb and Bi derivatives 3 and 4, which are supported by 3-center, 4-electron N-E-N bonds. Careful analysis of the solid-state structures of 1-5/[5-Me][OTf] in combination with NICS calculations (at the GIAO/M06/cc-pVTZ(-PP) level) and other computational methods (NBO) suggest that simpler NC chelates may support new phosphorus- and arsenic-containing heterocycles. Indeed, reduction of ECl2 (E = P or As) derivatives supported by N-Dipp (Dipp = 2,6-diisopropylphenyl) substituted NC bidentate ligands produced 1,2-benzoazaphosphole 11 and 1,2-benzoazaarsole 12. NICS calculations revealed 11 and 12 had aromatic character on par with that of pyrazole-based 5.	natural resonance theory; molecular-structure; metallacycle transfer; bond formation; phosphorus; complexes; carbon; chemistry; crystal; coordination

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