title: Nucleophilicity and P-C Bond Formation Reactions of a Terminal Phosphanido Iridium Complex.
abstract: The diiridium complex [{Ir(ABPN2)(CO)}2(μ-CO)] (1; [ABPN2](-) = [(allyl)B(Pz)2(CH2PPh2)](-)) reacts with diphenylphosphane affording [Ir(ABPN2)(CO)(H) (PPh2)] (2), the product of the oxidative addition of the P-H bond to the metal. DFT studies revealed a large contribution of the terminal phosphanido lone pair to the HOMO of 2, indicating nucleophilic character of this ligand, which is evidenced by reactions of 2 with typical electrophiles such as H(+), Me(+), and O2. Products from the reaction of 2 with methyl chloroacetate were found to be either [Ir(ABPN2)(CO)(H)(PPh2CH2CO2Me)][PF6] ([6]PF6) or [Ir(ABPN2)(CO)(Cl)(H)] (7) and the free phosphane (PPh2CH2CO2Me), both involving P-C bond formation, depending on the reaction conditions. New complexes having iridacyclophosphapentenone and iridacyclophosphapentanone moieties result from reactions of 2 with dimethyl acetylenedicarboxylate and dimethyl maleate, respectively, as a consequence of a further incorporation of the carbonyl ligand. In this line, the terminal alkyne methyl propiolate gave a mixture of a similar iridacyclophosphapentanone complex and [Ir(ABPN2){CH═C(CO2Me)-CO}{PPh2-CH═CH(CO2Me)}] (10), which bears the functionalized phosphane PPh2-CH═CH(CO2Me) and an iridacyclobutenone fragment. Related model reactions aimed to confirm mechanistic proposals are also studied.
authors.affiliation: Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC-Universidad de Zaragoza , Pedro Cerbuna 12, 50009-Zaragoza, Spain.
authors.forename: Ángel L
authors.initials: ÁL
authors.lastname: Serrano
authors.affiliation: Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC-Universidad de Zaragoza , Pedro Cerbuna 12, 50009-Zaragoza, Spain.
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Casado
authors.affiliation: Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC-Universidad de Zaragoza , Pedro Cerbuna 12, 50009-Zaragoza, Spain.
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Ciriano
authors.affiliation: Homogeneous and Supramolecular Catalysis, van't Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam , Science Park 904, 1098 XH Amsterdam, The Netherlands.
authors.forename: Bas
authors.initials: B
authors.lastname: de Bruin
authors.affiliation: Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC-Universidad de Zaragoza , Pedro Cerbuna 12, 50009-Zaragoza, Spain.
authors.forename: José A
authors.initials: JA
authors.lastname: López
authors.affiliation: Departamento de Química Inorgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC-Universidad de Zaragoza , Pedro Cerbuna 12, 50009-Zaragoza, Spain.
authors.forename: Cristina
authors.initials: C
authors.lastname: Tejel