Synthesis and Catalytic Applications of Heterobimetallic Carbene Complexes Obtained via Sequential Metalation of Two Bisazolium Salts
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http://dx.doi.org/10.1021/acs.organomet.9b00120 |
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Títol
Synthesis and Catalytic Applications of Heterobimetallic Carbene Complexes Obtained via Sequential Metalation of Two Bisazolium SaltsAutoria
Data de publicació
2019Editor
American Chemical SocietyISSN
0276-7333; 1520-6041Cita bibliogràfica
Maximilian Böhmer, Gregorio Guisado-Barrios, Florian Kampert, Florian Roelfes, Tristan Tsai Yuan Tan, Eduardo Peris, and F. Ekkehardt Hahn Organometallics 2019 38 (9), 2120-2131 DOI: 10.1021/acs.organomet.9b00120Tipus de document
info:eu-repo/semantics/articleVersió de l'editorial
https://pubs.acs.org/doi/10.1021/acs.organomet.9b00120Versió
info:eu-repo/semantics/publishedVersionResum
A simple sequential metalation approach starting
from the imidazolium/benzimidazolium salt 4(I)2 yielded the
heterobimetallic RhIII/M (M = PdII, IrI
, AuI
, RuII) complexes [6]−
[9]. Alternatively, a symmetrical ... [+]
A simple sequential metalation approach starting
from the imidazolium/benzimidazolium salt 4(I)2 yielded the
heterobimetallic RhIII/M (M = PdII, IrI
, AuI
, RuII) complexes [6]−
[9]. Alternatively, a symmetrical 1,3-imidazolium substituted
benzene was used for the preparation of the heterobimetallic
M′/PdII (M′ = RhIII, IrIII) complexes [12] and [13]. The versatile
stepwise approach used for the preparation of complexes [6]−[9]
involved the deprotonation reaction of the bisazolium salt 4(I)2 in
the presence of [RhCp*(Cl)2]2 to afford the monometallic
complex [5]I featuring a chelating coordinated bidentate
CNHC^Cphenyl ligand. Complex [5]I was reacted with Ag2O to
give a nonisolated RhIII/AgI complex which in a subsequent
transmetalation reaction yielded the heterobimetallic RhIII/M bisNHC complexes (M = PdII [6], IrI [7], AuI [8], RuII [9]).
Similarly, heterobimetallic M′/PdII bis-NHC complexes [12] (M′ = RhIII) and [13] (M′ = IrIII) have been prepared from a
symmetrical bisazolium salt by generating first the monometallic M′ complexes followed by a transmetalation reaction of the in
situ generated M′/AgI complexes with [Pd(dmba)(μ-Cl)]2. The RhIII/PdII complexes [6] and [12] and the IrIII/PdII complex
[13] were used as catalysts for two orthogonal tandem reactions, namely, the Suzuki−Miyaura coupling/transfer hydrogenation
and the Suzuki−Miyaura-coupling/α-alkylation of ketones. The catalytic activity of the heterobimetallic complexes was
compared to mixtures of the related monometallic analogues [14]−[17], with the heterobimetallic complexes generally showing
a higher catalytic activity. In addition, nBuOH was found to play a dual role as an alkylating and reducing agent in the Suzuki−
Miyaura coupling/α-alkylation of ketones. [-]
Publicat a
Organometallics 2019 38 (9)Proyecto de investigación
UJI-B2017-07 ; SFB 858 and IRTG 2027 ; GGB, IJCI2015-23407Drets d'accés
http://rightsstatements.org/vocab/CNE/1.0/
info:eu-repo/semantics/restrictedAccess
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