TY - JOUR
T1 - Base-Promoted, Remote C-H Activation at a Cationic (n 5 -C 5 Me 5 )Ir(III) Center Involving Reversible C-C Bond Formation of Bound C 5 Me 5
AU - Moreno, Juan J.
AU - Espada, María F.
AU - Campos, Jesús
AU - López-Serrano, Joaquín
AU - Macgregor, Stuart A.
AU - Carmona, Ernesto
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/2/13
Y1 - 2019/2/13
N2 - C-H bond activation at cationic [(n 5 -C 5 Me 5 )Ir(PMe 2 Ar′)] centers is described, where PMe 2 Ar′ are the terphenyl phosphine ligands PMe 2 Ar Xyl 2 and PMe 2 Ar Dipp 2 . Different pathways are defined for the conversion of the five-coordinate complexes [(n 5 -C 5 Me 5 )IrCl(PMe 2 Ar′)] + , 2(Xyl) + and 2(Dipp) + , into the corresponding pseudoallyls 3(Xyl) + and 3(Dipp) + . In the absence of an external Brønsted base, electrophilic, remote ζ C-H activation takes place, for which the participation of dicationic species, [(n 5 -C 5 Me 5 )Ir(PMe 2 Ar′)] 2+ , is proposed. When NEt 3 is present, the PMe 2 Ar Dipp 2 system is shown to proceed via 4(Dipp) + as an intermediate en route to the thermodynamic, isomeric product 3(Dipp) + . This complex interconversion involves a non-innocent C 5 Me 5 ligand, which participates in C-H and C-C bond formation and cleavage. Remarkably, the conversion of 4(Dipp) + to 3(Dipp) + also proceeds in the solid state.
AB - C-H bond activation at cationic [(n 5 -C 5 Me 5 )Ir(PMe 2 Ar′)] centers is described, where PMe 2 Ar′ are the terphenyl phosphine ligands PMe 2 Ar Xyl 2 and PMe 2 Ar Dipp 2 . Different pathways are defined for the conversion of the five-coordinate complexes [(n 5 -C 5 Me 5 )IrCl(PMe 2 Ar′)] + , 2(Xyl) + and 2(Dipp) + , into the corresponding pseudoallyls 3(Xyl) + and 3(Dipp) + . In the absence of an external Brønsted base, electrophilic, remote ζ C-H activation takes place, for which the participation of dicationic species, [(n 5 -C 5 Me 5 )Ir(PMe 2 Ar′)] 2+ , is proposed. When NEt 3 is present, the PMe 2 Ar Dipp 2 system is shown to proceed via 4(Dipp) + as an intermediate en route to the thermodynamic, isomeric product 3(Dipp) + . This complex interconversion involves a non-innocent C 5 Me 5 ligand, which participates in C-H and C-C bond formation and cleavage. Remarkably, the conversion of 4(Dipp) + to 3(Dipp) + also proceeds in the solid state.
UR - http://www.scopus.com/inward/record.url?scp=85061484925&partnerID=8YFLogxK
U2 - 10.1021/jacs.8b11752
DO - 10.1021/jacs.8b11752
M3 - Article
C2 - 30682245
AN - SCOPUS:85061484925
SN - 0002-7863
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
ER -