Heavy metalla vinyl-cations show metal–Lewis acid cooperativity in reaction with small molecules (NH3, N2H4, H2O, H2)

Maximilian Auer; Janina Bolten; Klaus Eichele; Hartmut Schubert; Christian P. Sindlinger; Lars Wesemann

doi:10.1039/D2SC05620H

Heavy metalla vinyl-cations show metal–Lewis acid cooperativity in reaction with small molecules (NH₃, N₂H₄, H₂O, H₂)†

Maximilian Auer,^a Janina Bolten,^a Klaus Eichele,^a Hartmut Schubert,^a Christian P. Sindlinger

*^b and Lars Wesemann

*^a

Author affiliations

* Corresponding authors

^a Institut für Anorganische Chemie, Auf der Morgenstelle 18, 72076 Tübingen, Germany
E-mail: lars.wesemann@uni-tuebingen.de

^b Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
E-mail: christian.sindlinger@iac.uni-stuttgart.de

Abstract

Halide abstraction from tetrylidene complexes [TbbE(Br)IrH(PMe₃)₃] [E = Ge (1), Sn (2)] and [Ar*E(Cl)IrH(PMe₃)₃] gives the salts [TbbEIrH(PMe₃)₃][BAr^F₄] [E = Ge (3), Sn (4)] and [Ar*EIrH(PMe₃)₃][BAr^F₄] [E = Ge (3′), E = Sn (4′)] (Tbb = 2,6-[CH(SiMe₃)₂]₂-4-(t-Bu)C₆H₂, Ar* = 2,6-Trip₂C₆H₃, Trip = 2,4,6-triisopropylphenyl). Bonding analysis suggests their most suitable description as metalla-tetrela vinyl cations with an Ir [double bond, length as m-dash] E double bond and a near linear coordination at the Ge/Sn atoms. Cationic complexes 3 and 4 oxidatively add NH₃, N₂H₄, H₂O, HCl, and H₂ selectively to give: [TbbGe(NH₂)IrH₂(PMe₃)₃][BAr^F₄] (5), [TbbE(NHNH₂)IrH₂(PMe₃)₃][BAr^F₄] [E = Ge (7), Sn (8)], [TbbE(OH)IrH₂(PMe₃)₃][BAr^F₄] [E = Ge (9), Sn (10)], [TbbE(Cl)IrH₂(PMe₃)₃][BAr^F₄] [E = Ge (11a), Sn (12a)], [TbbGe(H)IrH₂(PMe₃)₃][BAr^F₄] (13), [TbbSn(μ-H₃)Ir(PMe₃)₃][BAr^F₄] (14), and [TbbSn(H)IrH₂(PMe₃)₃][BAr^F₄] (15). 14 isomerizes to give 15via an 1,2-H shift reaction. Hydride addition to cation 3 gives a mixture of products [TbbGeHIrH(PMe₃)₃] (16) and [TbbGeIrH₂(PMe₃)₃] (17) and a reversible 1,2-H shift between 16 and 17 was studied. In the tin case 4 the dihydride [TbbSnIrH₂(PMe₃)₃] (18) was isolated exclusively. The PMe₃ and PEt₃ derivatives, 18 and [TbbSnIrH₂(PEt₃)₃] (19), respectively, could also be synthesized in reaction of [TbbSnH₂]⁻ with the respective chloride [(R₃P)_nIrCl] (R = Me, n = 4; R = Et, n = 3). Reaction of complex 19 with CO gives the substitution product [TbbSnIrH₂(CO)(PEt₃)₂] (20). Further reaction with CO results in hydrogen transfer from the iridium to the tin atom to give [TbbSnH₂Ir(CO)₂(PEt₃)₂] (21). The reversibility of this ligand induced reductive elimination transferring 20 to 21 is shown.

This article is part of the themed collection: 2023 Chemical Science HOT Article Collection

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DOI: https://doi.org/10.1039/D2SC05620H
Article type: Edge Article
Submitted: 10 Oct 2022
Accepted: 24 Nov 2022
First published: 24 Nov 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry

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Chem. Sci., 2023,14, 514-524

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Heavy metalla vinyl-cations show metal–Lewis acid cooperativity in reaction with small molecules (NH₃, N₂H₄, H₂O, H₂)

M. Auer, J. Bolten, K. Eichele, H. Schubert, C. P. Sindlinger and L. Wesemann, Chem. Sci., 2023, 14, 514 DOI: 10.1039/D2SC05620H

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