Heavy Metalla Vinyl-Cations show Metal-Lewis Acid Cooperativity in Reaction with Small Molecules (NH3, N2H4, H2O, H2)

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][BArF4] [E =Ge (3), Sn (4)] and [Ar*EIrH(PMe3)3][BArF4] [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 a Ir=E double bond and a near linear coordination at the Ge/Sn atoms. Cationic complexes 3 and 4 oxidatively add NH3, N2H4, H2O, HCl∙Et2O, and H2 selectively to give: [TbbGe(NH2)IrH2(PMe3)3][BArF4] (5), [TbbE(NHNH2)IrH2(PMe3)3][BArF4] [E = Ge (7), Sn(8)], [TbbE(OH)IrH2(PMe3)3][BArF4] [E = Ge (9), Sn(10)], [TbbE(Cl)IrH2(PMe3)3][BArF4] [E = Ge (11a), Sn(12a)], [TbbGe(H)IrH2(PMe3)3][BArF4] (13), [TbbSn(µ-H3)Ir(PMe3)3][BArF4] (14), and [TbbSnHIrH2(PMe3)3][BArF4] (15). 14 isomerizes to give 15 via 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 1,2H-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.

Supplementary files

Article information

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
Creative Commons BY-NC license

Chem. Sci., 2022, Accepted Manuscript

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., 2022, Accepted Manuscript , DOI: 10.1039/D2SC05620H

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