title: A pentacoordinated norbornenyl-acyl-rhodium(iii) complex as a likely intermediate in the catalytic hydroacylation of norbornadiene.
abstract: [RhCl(NCO)(nbyl)(PR3)] (nbyl = σ-norbornenyl; NCO = quinoline-8-acyl; R = p-F-C6H4) (1) has been synthesized by the reaction of [Rh(nbd)Cl]2(nbd = norbornadiene) with 2 equivalents of NCHO (quinoline-8-carbaldehyde) and 2 equivalents of PR3. Compound 1 has been fully characterized in solution and also in the solid state by X-ray diffraction. Compound 1 shows low stability in solution and undergoes slow ring closure isomerization to [RhCl(NCO)(ntyl)(PR3)] (ntyl = σ-nortricyclyl) (2) after 12 hours. Reaction of 1 with an extra equivalent of aldehyde (NCHO) and PR3led to the formation of [RhCl(H)(NCO)(PR3)2] (3) and an equivalent of ketone, which is a hydroacylation product. The catalytic activity of 3 in the hydroacylation of nbd with NCHO is reported as well as the catalytic activity of compound 1. Compounds 1 and 3 are proposed as intermediate species in the catalytic hydroacylation of norbornadiene with NCHO.
authors: Facultad de Química de San Sebastián, Universidad del País Vasco (UPV/EHU), Apartado 1072, 20080, San Sebastián, Spain. miguelangel.huertos@ehu.es mariaangeles.garralda@ehu.es.
authors: N
authors: N
authors: Almenara
authors: Facultad de Química de San Sebastián, Universidad del País Vasco (UPV/EHU), Apartado 1072, 20080, San Sebastián, Spain. miguelangel.huertos@ehu.es mariaangeles.garralda@ehu.es.
authors: L
authors: L
authors: Ibarlucea
authors: Facultad de Química de San Sebastián, Universidad del País Vasco (UPV/EHU), Apartado 1072, 20080, San Sebastián, Spain. miguelangel.huertos@ehu.es mariaangeles.garralda@ehu.es.
authors: C
authors: C
authors: Mendicute-Fierro
authors: Facultad de Química de San Sebastián, Universidad del País Vasco (UPV/EHU), Apartado 1072, 20080, San Sebastián, Spain. miguelangel.huertos@ehu.es mariaangeles.garralda@ehu.es.
authors: J M
authors: JM
authors: Seco
authors: Departamento de Química Inorgánica, Universidad de Granada, Avenida Fuentenueva s/n, 18071 Granada, Spain.
authors: A
authors: A
authors: Rodríguez-Diéguez
authors: Facultad de Química de San Sebastián, Universidad del País Vasco (UPV/EHU), Apartado 1072, 20080, San Sebastián, Spain. miguelangel.huertos@ehu.es mariaangeles.garralda@ehu.es.
authors: M A
authors: MA
authors: Garralda
authors: Facultad de Química de San Sebastián, Universidad del País Vasco (UPV/EHU), Apartado 1072, 20080, San Sebastián, Spain. miguelangel.huertos@ehu.es mariaangeles.garralda@ehu.es and IKERBASQUE, Basque Fundation for Science, 48011, Bilbao, Spain.
authors: M A
authors: http://orcid.org/0000-0002-5315-5642
authors: MA
authors: Huertos