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Heavy metalla vinyl-cations show metal–Lewis acid cooperativity in reaction with small molecules (NH(3), N(2)H(4), H(2)O, H(2))
Halide abstraction from tetrylidene complexes [TbbE(Br)IrH(PMe(3))(3)] [E = Ge (1), Sn (2)] and [Ar*E(Cl)IrH(PMe(3))(3)] gives the salts [TbbEIrH(PMe(3))(3)][BAr(F)(4)] [E = Ge (3), Sn (4)] and [Ar*EIrH(PMe(3))(3)][BAr(F)(4)] [E = Ge (3′), E = Sn (4′)] (Tbb = 2,6-[CH(SiMe(3))(2)](2)-4-(t-Bu)C(6)H(2)...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
The Royal Society of Chemistry
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9847682/ https://www.ncbi.nlm.nih.gov/pubmed/36741530 http://dx.doi.org/10.1039/d2sc05620h |
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author | Auer, Maximilian Bolten, Janina Eichele, Klaus Schubert, Hartmut Sindlinger, Christian P. Wesemann, Lars |
author_facet | Auer, Maximilian Bolten, Janina Eichele, Klaus Schubert, Hartmut Sindlinger, Christian P. Wesemann, Lars |
author_sort | Auer, Maximilian |
collection | PubMed |
description | Halide abstraction from tetrylidene complexes [TbbE(Br)IrH(PMe(3))(3)] [E = Ge (1), Sn (2)] and [Ar*E(Cl)IrH(PMe(3))(3)] gives the salts [TbbEIrH(PMe(3))(3)][BAr(F)(4)] [E = Ge (3), Sn (4)] and [Ar*EIrH(PMe(3))(3)][BAr(F)(4)] [E = Ge (3′), E = Sn (4′)] (Tbb = 2,6-[CH(SiMe(3))(2)](2)-4-(t-Bu)C(6)H(2), Ar* = 2,6-Trip(2)C(6)H(3), 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 NH(3), N(2)H(4), H(2)O, HCl, and H(2) selectively to give: [TbbGe(NH(2))IrH(2)(PMe(3))(3)][BAr(F)(4)] (5), [TbbE(NHNH(2))IrH(2)(PMe(3))(3)][BAr(F)(4)] [E = Ge (7), Sn (8)], [TbbE(OH)IrH(2)(PMe(3))(3)][BAr(F)(4)] [E = Ge (9), Sn (10)], [TbbE(Cl)IrH(2)(PMe(3))(3)][BAr(F)(4)] [E = Ge (11a), Sn (12a)], [TbbGe(H)IrH(2)(PMe(3))(3)][BAr(F)(4)] (13), [TbbSn(μ-H(3))Ir(PMe(3))(3)][BAr(F)(4)] (14), and [TbbSn(H)IrH(2)(PMe(3))(3)][BAr(F)(4)] (15). 14 isomerizes to give 15via an 1,2-H shift reaction. Hydride addition to cation 3 gives a mixture of products [TbbGeHIrH(PMe(3))(3)] (16) and [TbbGeIrH(2)(PMe(3))(3)] (17) and a reversible 1,2-H shift between 16 and 17 was studied. In the tin case 4 the dihydride [TbbSnIrH(2)(PMe(3))(3)] (18) was isolated exclusively. The PMe(3) and PEt(3) derivatives, 18 and [TbbSnIrH(2)(PEt(3))(3)] (19), respectively, could also be synthesized in reaction of [TbbSnH(2)](−) with the respective chloride [(R(3)P)(n)IrCl] (R = Me, n = 4; R = Et, n = 3). Reaction of complex 19 with CO gives the substitution product [TbbSnIrH(2)(CO)(PEt(3))(2)] (20). Further reaction with CO results in hydrogen transfer from the iridium to the tin atom to give [TbbSnH(2)Ir(CO)(2)(PEt(3))(2)] (21). The reversibility of this ligand induced reductive elimination transferring 20 to 21 is shown. |
format | Online Article Text |
id | pubmed-9847682 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | The Royal Society of Chemistry |
record_format | MEDLINE/PubMed |
spelling | pubmed-98476822023-02-03 Heavy metalla vinyl-cations show metal–Lewis acid cooperativity in reaction with small molecules (NH(3), N(2)H(4), H(2)O, H(2)) Auer, Maximilian Bolten, Janina Eichele, Klaus Schubert, Hartmut Sindlinger, Christian P. Wesemann, Lars Chem Sci Chemistry Halide abstraction from tetrylidene complexes [TbbE(Br)IrH(PMe(3))(3)] [E = Ge (1), Sn (2)] and [Ar*E(Cl)IrH(PMe(3))(3)] gives the salts [TbbEIrH(PMe(3))(3)][BAr(F)(4)] [E = Ge (3), Sn (4)] and [Ar*EIrH(PMe(3))(3)][BAr(F)(4)] [E = Ge (3′), E = Sn (4′)] (Tbb = 2,6-[CH(SiMe(3))(2)](2)-4-(t-Bu)C(6)H(2), Ar* = 2,6-Trip(2)C(6)H(3), 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 NH(3), N(2)H(4), H(2)O, HCl, and H(2) selectively to give: [TbbGe(NH(2))IrH(2)(PMe(3))(3)][BAr(F)(4)] (5), [TbbE(NHNH(2))IrH(2)(PMe(3))(3)][BAr(F)(4)] [E = Ge (7), Sn (8)], [TbbE(OH)IrH(2)(PMe(3))(3)][BAr(F)(4)] [E = Ge (9), Sn (10)], [TbbE(Cl)IrH(2)(PMe(3))(3)][BAr(F)(4)] [E = Ge (11a), Sn (12a)], [TbbGe(H)IrH(2)(PMe(3))(3)][BAr(F)(4)] (13), [TbbSn(μ-H(3))Ir(PMe(3))(3)][BAr(F)(4)] (14), and [TbbSn(H)IrH(2)(PMe(3))(3)][BAr(F)(4)] (15). 14 isomerizes to give 15via an 1,2-H shift reaction. Hydride addition to cation 3 gives a mixture of products [TbbGeHIrH(PMe(3))(3)] (16) and [TbbGeIrH(2)(PMe(3))(3)] (17) and a reversible 1,2-H shift between 16 and 17 was studied. In the tin case 4 the dihydride [TbbSnIrH(2)(PMe(3))(3)] (18) was isolated exclusively. The PMe(3) and PEt(3) derivatives, 18 and [TbbSnIrH(2)(PEt(3))(3)] (19), respectively, could also be synthesized in reaction of [TbbSnH(2)](−) with the respective chloride [(R(3)P)(n)IrCl] (R = Me, n = 4; R = Et, n = 3). Reaction of complex 19 with CO gives the substitution product [TbbSnIrH(2)(CO)(PEt(3))(2)] (20). Further reaction with CO results in hydrogen transfer from the iridium to the tin atom to give [TbbSnH(2)Ir(CO)(2)(PEt(3))(2)] (21). The reversibility of this ligand induced reductive elimination transferring 20 to 21 is shown. The Royal Society of Chemistry 2022-11-24 /pmc/articles/PMC9847682/ /pubmed/36741530 http://dx.doi.org/10.1039/d2sc05620h Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/ |
spellingShingle | Chemistry Auer, Maximilian Bolten, Janina Eichele, Klaus Schubert, Hartmut Sindlinger, Christian P. Wesemann, Lars Heavy metalla vinyl-cations show metal–Lewis acid cooperativity in reaction with small molecules (NH(3), N(2)H(4), H(2)O, H(2)) |
title | Heavy metalla vinyl-cations show metal–Lewis acid cooperativity in reaction with small molecules (NH(3), N(2)H(4), H(2)O, H(2)) |
title_full | Heavy metalla vinyl-cations show metal–Lewis acid cooperativity in reaction with small molecules (NH(3), N(2)H(4), H(2)O, H(2)) |
title_fullStr | Heavy metalla vinyl-cations show metal–Lewis acid cooperativity in reaction with small molecules (NH(3), N(2)H(4), H(2)O, H(2)) |
title_full_unstemmed | Heavy metalla vinyl-cations show metal–Lewis acid cooperativity in reaction with small molecules (NH(3), N(2)H(4), H(2)O, H(2)) |
title_short | Heavy metalla vinyl-cations show metal–Lewis acid cooperativity in reaction with small molecules (NH(3), N(2)H(4), H(2)O, H(2)) |
title_sort | heavy metalla vinyl-cations show metal–lewis acid cooperativity in reaction with small molecules (nh(3), n(2)h(4), h(2)o, h(2)) |
topic | Chemistry |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9847682/ https://www.ncbi.nlm.nih.gov/pubmed/36741530 http://dx.doi.org/10.1039/d2sc05620h |
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