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> Synthesis and reactivity of an iridium complex based on a tridentate aminophosphano ligand
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Synthesis and reactivity of an iridium complex based on a tridentate aminophosphano ligand
Palmese, M.
(Universidad de Zaragoza)
;
Pérez-Torrente, J. J.
(Universidad de Zaragoza)
;
Passarelli, V.
Resumen:
The iridium(iii) hydride compound IrH{¿3C, P, P'-(SiNP-H)}(CNtBu)2]PF6] (1PF6) was obtained by reaction of Ir(SiNP)(cod)]PF6] with CNtBu as the result of the intramolecular oxidative addition of the SiCH2-H bond to iridium(i) SiNP = Si(CH3)2{N(4-tolyl)PPh2}2, SiNP-H = CH2Si(CH3){N(4-tolyl)PPh2}2]. The mechanism of the reaction was investigated by NMR spectroscopy and DFT calculations showing that the pentacoordinated intermediate Ir(SiNP)(cod)(CNtBu)]PF6] (2PF6) forms in the first place and that further reacts with CNtBu, affording the square planar intermediate Ir(SiNP)(CNtBu)2]PF6] (3PF6) that finally undergoes the intramolecular oxidative addition of the SiCH2-H bond. The reactivity of 1PF6 was investigated. On one hand, the reaction of 1PF6 with N-chlorosuccinimide or N-bromosuccinimide provides the haloderivatives IrX{¿3C, P, P'-(SiNP-H)}(CNtBu)2]PF6] (X = Cl, 4PF6; Br, 5PF6), and the reaction of 5PF6 with AgPF6 in the presence of acetonitrile affords the solvato species Ir{¿3C, P, P'-(SiNP-H)}(CH3CN)(CNtBu)2]2+ (62+) isolated as the hexafluorophosphate salt. On the other hand, the reaction of 1PF6 with HBF4 gives the iridium(iii) compound IrH(CH2SiF2CH3)(HNP)2(CNtBu)2]BF4] (7BF4) as the result of the formal addition of hydrogen fluoride to the Si-N bonds of 1+ HNP = HN(4-tolyl)PPh2]. A similar outcome was observed in the reaction of 1PF6 with CF3COOH rendering 7PO2F2. In this case the intermediate IrH{¿2C, P-CH2SiMeFN(4-tolyl)PPh2}(HNP)(CNtBu)2]+ (8+) was observed and characterised in situ by NMR spectroscopy. DFT calculations suggests that the reaction goes through the sequential protonation of the nitrogen atom of the Si-N-P moiety followed by the formal addition of fluoride ion to silicon. Also, the crystal structures of SiNP, 1PF6, 4PF6 and 7BF4 have been determined by X-ray diffraction measurements. © 2022 The Royal Society of Chemistry
Idioma:
Inglés
DOI:
10.1039/d2dt00794k
Año:
2022
Publicado en:
Dalton Transactions
51 (2022), 7142 - 7153
ISSN:
1477-9226
Factor impacto JCR:
4.0 (2022)
Categ. JCR:
CHEMISTRY, INORGANIC & NUCLEAR
rank: 7 / 42 = 0.167
(2022)
- Q1
- T1
Factor impacto CITESCORE:
7.1 -
Chemistry
(Q1)
Factor impacto SCIMAGO:
0.79 -
Inorganic Chemistry
(Q1)
Financiación:
info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20R
Financiación:
info:eu-repo/grantAgreement/ES/MICINN/PID2019-103965GB-I00/AEI/10.13039/501100011033
Tipo y forma:
Artículo (PostPrint)
Área (Departamento):
Área Química Inorgánica
(
Dpto. Química Inorgánica
)
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Exportado de SIDERAL (2024-03-18-12:58:15)
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Registro creado el 2023-04-21, última modificación el 2024-03-19
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