Sn,P-Peri-Substituted Naphthalene as a Ligand for Transition Metals

Michal Aman, Libor Dostal, Zdenka Ruzickova, Jan Turek, Roman Jambor

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Peri-substituted naphthalene 1-PPh2-8-SnL-C10H6 (1) [L = 2,6-(Me2NCH2)2C6H3] was used as a ligand for the complexation of transition metals (TMs). The presence of two donor atoms provided rigid κ2P,Sn-coordinated complexes of TM. Correspondingly, reactions of 1 with binuclear Mn2(CO)10 and Co2(CO)8 yielded ionic complexes [(κ2-1)Mn(CO)4]+ [Mn(CO)5]− (2) and [(κ2-1)Co(CO)3]+ [Co(CO)4]− (3), first examples of Sn-coordinated Mn(CO)4+ and Co(CO)3+ cations. The reactivity of 1 toward TM–Cl complexes is quite different. During these reactions, transmetallation with subsequent elimination of L(Cl)Sn was observed. However, L(Cl)Sn remained in the coordination sphere of the TM, yielding P-coordinated heterobimetallic TM complexes 1-PPh2-8-[Rh(COD){Sn(Cl)L}]C10H6 (7), 1-PPh2-8-[Ir(COD){Sn(Cl)L}]C10H6 (8), and 1-PPh2-8-[Pd(Cl){Sn(Cl)L}]-C10H6 (9) with additional Sn→TM intermolecular coordination. These transmetallations may be kinetically driven, as suggested by density functional theory calculations and isolation of the κ2P,Sn-coordinated complex of PtCl2, [(κ2-1)PtCl2] (10). Thus, the reactivity of 1 clearly deviates from the P,Sn-based ligands studied so far.
Originele taal-2English
Pagina's (van-tot)2327-2341
Aantal pagina's15
TijdschriftOrganometallics
Volume41
Nummer van het tijdschrift16
DOI's
StatusPublished - 22 aug 2022

Bibliografische nota

Funding Information:
J.T. gratefully acknowledges the financial support of the Research Foundation-Flanders (FWO; project no. 12Y7721N) and the computational resources and services provided by the VSC (Flemish Supercomputer Center), funded by the FWO and the Flemish Government. R.J. gratefully acknowledges the Czech Science foundation (project 22-07635S) for financial support

Publisher Copyright:
© 2022 American Chemical Society. All rights reserved.

Copyright:
Copyright 2022 Elsevier B.V., All rights reserved.

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