Exploring the Transphobia Effect on Heteroleptic NHC Cycloplatinated Complexes
Resumen: The synthesis of 1-(4-cyanophenyl)-1H-imidazol (1) has been carried out by an improved method. Then its corresponding imidazolium iodide salt, 2, has been used to prepare the N-heterocyclic carbene (NHC) cycloplatinated compound {Pt(µ-Cl)(CC*)}2] (4) (HCC*-¿C* = 1-(4-cyanophenyl)-3-methyl-1H-imidazol-2-ylidene) following a step-by-step protocol. The intermediate complex PtCl(¿3-2-Me-C3H4) (HCC*-¿C*)] (3) has also been isolated and characterized. Using 4 as precursor, several heteroleptic complexes of stoicheometry PtCl(CC*)L] (L = PPh3 (5), pyridine (py, 6), 2, 6-dimethylphenyl isocyanide (CNXyl, 7), and 2-mercapto-1-methylimidazole (MMI, 8)) and Pt(CC*)LL']PF6 (L = PPh3, L' = py (9), CNXyl (10), and MMI (11)) have been synthesized. Complexes 6-8 were obtained as a mixture of cis- and trans-(C*, L) isomers, while trans-(C*, L) isomer was the only one observed for complexes 5 and 9-11. Their geometries have been discussed in terms of the degree of transphobia (T) of pairs of trans ligands and supported by theoretical calculations. The trans influence of the two s Pt-C bonds present in these molecules, Pt-CAr and Pt-C*(NHC), has been compared from the JPt-P values observed in the new complex Pt(CC*)(dppe)]PF6 (dppe = 1, 2-bis(diphenylphosphino)ethane, 12).
Idioma: Inglés
DOI: 10.1021/acs.inorgchem.5b01655
Año: 2015
Publicado en: Inorganic Chemistry 54, 20 (2015), 9885-9895
ISSN: 0020-1669

Factor impacto JCR: 4.82 (2015)
Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 4 / 46 = 0.087 (2015) - Q1 - T1
Factor impacto SCIMAGO: 1.782 - Chemistry (miscellaneous) (Q1) - Physical and Theoretical Chemistry (Q1) - Inorganic Chemistry (Q1)

Tipo y forma: Article (PostPrint)

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