Synthesis of Cobalt-Tin and -Lead Tetrylidynes-Reactivity Study of the Triple Bond.

Autor: Auer M; Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076, Tübingen, Germany., Zwettler K; Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076, Tübingen, Germany., Eichele K; Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076, Tübingen, Germany., Schubert H; Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076, Tübingen, Germany., Sindlinger CP; Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569, Stuttgart, Germany., Wesemann L; Institut für Anorganische Chemie, Eberhard Karls Universität Tübingen, Auf der Morgenstelle 18, 72076, Tübingen, Germany.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2023 Aug 28; Vol. 62 (35), pp. e202305951. Date of Electronic Publication: 2023 Jul 21.
DOI: 10.1002/anie.202305951
Abstrakt: Tetrylidynes [TbbSn≡Co(PMe 3 ) 3 ] (1 a) and [TbbPb≡Co(PMe 3 ) 3 ] (2) (Tbb=2,6-[CH(SiMe 3 ) 2 ] 2 -4-(t-Bu)C 6 H 2 ) are accessed for the first time via a substitution reaction between [Na(OEt 2 )][Co(PMe 3 ) 4 ] and [Li(thf) 2 ][TbbEBr 2 ] (E=Sn, Pb). Following an alternative procedure the stannylidyne [Ar*Sn≡Co(PMe 3 ) 3 ] (1 b) was synthesized by hydrogen atom abstraction using AIBN from the paramagnetic hydride complex [Ar*SnH=Co(PMe 3 ) 3 ] (4) (AIBN=azobis(isobutyronitrile)). The stannylidyne 1 a adds two equivalents of water to yield the dihydroxide [TbbSn(OH) 2 CoH 2 (PMe 3 ) 3 ] (5). In reaction of the stannylidyne 1 a with CO 2 a product of a redox reaction [TbbSn(CO 3 )Co(CO)(PMe 3 ) 3 ] (6) was isolated. Protonation of the tetrylidynes occurs at the cobalt atom to give the metalla-stanna vinyl cation [TbbSn=CoH(PMe 3 ) 3 ][BAr F 4 ] (7 a) [Ar F =C 6 H 3 -3,5-(CF 3 ) 2 ]. The analogous germanium and tin cations [Ar*E=CoH(PMe 3 ) 3 ][BAr F 4 ] (E=Ge 9, Sn 7 b) (Ar*=C 6 H 3 (2,6-Trip) 2 , Trip=2,4,6-C 6 H 2 iPr 3 ) were also obtained by oxidation of the paramagnetic complexes [Ar*EH=Co(PMe 3 ) 3 ] (E=Ge 3, Sn 4), which were synthesized by substitution of a PMe 3 ligand of [Co(PMe 3 ) 4 ] by a hydridoylene (Ar*EH) unit.
(© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)
Databáze: MEDLINE
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