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• W2217922018 endingPage "839" @default.
• W2217922018 startingPage "828" @default.
• W2217922018 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." @default.
• W2217922018 created "2016-06-24" @default.
• W2217922018 creator A5001644383 @default.
• W2217922018 creator A5029252935 @default.
• W2217922018 creator A5030852150 @default.
• W2217922018 creator A5031291421 @default.
• W2217922018 creator A5065885946 @default.
• W2217922018 creator A5079818941 @default.
• W2217922018 date "2015-12-22" @default.
• W2217922018 modified "2023-10-15" @default.
• W2217922018 title "Nucleophilicity and P–C Bond Formation Reactions of a Terminal Phosphanido Iridium Complex" @default.
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