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Title

Nucleophilicity and P-C bond formation reactions of a terminal phosphanido iridium complex

AuthorsSerrano, Ángel L. ; Casado, Miguel A. ; Ciriano, Miguel A. ; Bruin, Bas de; López, José A. ; Tejel, Cristina
Issue Date2016
PublisherAmerican Chemical Society
CitationInorganic Chemistry 55(2): 828-839 (2016)
AbstractThe 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.
Publisher version (URL)https://doi.org/10.1021/acs.inorgchem.5b02301
URIhttp://hdl.handle.net/10261/154912
DOIhttp://dx.doi.org/10.1021/acs.inorgchem.5b02301
Identifiersdoi: 10.1021/acs.inorgchem.5b02301
e-issn: 1520-510X
issn: 0020-1669
Appears in Collections:(ISQCH) Artículos
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