Facile Access to Cationic Methylstannylenes and Silylenes Stabilized by E-Pt Bonding and their Methyl Group Transfer Reactivity.

Autor: Govindarajan R; Okinawa Institute of Science and Technology Graduate University, 1919-1 Tancha, Onna-son, Okinawa, 904-0495, Japan., Fayzullin RR; Arbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center, Russian Academy of Sciences, 8 Arbuzov Street, Kazan, 420088, Russian Federation., Deolka S; Okinawa Institute of Science and Technology Graduate University, 1919-1 Tancha, Onna-son, Okinawa, 904-0495, Japan., Khaskin E; Okinawa Institute of Science and Technology Graduate University, 1919-1 Tancha, Onna-son, Okinawa, 904-0495, Japan., Vasylevskyi S; Okinawa Institute of Science and Technology Graduate University, 1919-1 Tancha, Onna-son, Okinawa, 904-0495, Japan., Vardhanapu PK; Okinawa Institute of Science and Technology Graduate University, 1919-1 Tancha, Onna-son, Okinawa, 904-0495, Japan., Pal S; Okinawa Institute of Science and Technology Graduate University, 1919-1 Tancha, Onna-son, Okinawa, 904-0495, Japan., Khusnutdinova JR; Okinawa Institute of Science and Technology Graduate University, 1919-1 Tancha, Onna-son, Okinawa, 904-0495, Japan.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2024 Feb 07; Vol. 30 (8), pp. e202303789. Date of Electronic Publication: 2023 Dec 14.
DOI: 10.1002/chem.202303789
Abstrakt: We describe a family of cationic methylstannylene and chloro- and azidosilylene organoplatinum(II) complexes supported by a neutral, binucleating ligand. Methylstannylenes MeSn: + are stabilized by coordination to Pt II and are formed by facile Me group transfer from dimethyl or monomethyl Pt II complexes, in the latter case triggered by concomitant B-H, Si-H, and H 2 bond activation that involves hydride transfer from Sn to Pt. A cationic chlorosilylene complex was obtained by formal HCl elimination and Cl - removal from HSiCl 3 under ambient conditions. The computational studies show that stabilization of cationic methylstannylenes and cationic silylenes is achieved through weak coordination to a neutral N-donor ligand binding pocket. The analysis of the electronic potentials, as well as the Laplacian of electron density, also reveals the differences in the character of Pt-Si vs. Pt-Sn bonding. We demonstrate the importance of a ligand-supported binuclear Pt/tetrel core and weak coordination to facilitate access to tetrylium-ylidene Pt complexes, and a transmetalation approach to the synthesis of MeSn II : + derivatives.
(© 2023 Wiley-VCH GmbH.)
Databáze: MEDLINE
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