Mild oxidation of C-C bonds of benzoiridacycles

Rosa Padilla; Verónica Salazar; Margarita Paneque; José G. Alvarado-Rodríguez; Joaquín Tamariz; Héctor Pacheco-Cuvas; Florencia Vattier

doi:10.1021/om100196h

Mild oxidation of C-C bonds of benzoiridacycles

Rosa Padilla, Verónica Salazar, Margarita Paneque, José G. Alvarado-Rodríguez, Joaquín Tamariz, Héctor Pacheco-Cuvas, Florencia Vattier

Escuela Nacional de Ciencias Biológicas (ENCB)

Research output: Contribution to journal › Article › peer-review

9 Scopus citations

Abstract

We describe herein the formation of two metallacyclic derivatives, 4b and 5b, which contain a coordinated ketone functionality (from an ?-keto ester metallacyclic substituent). An iridafuran, 6, that results from the reaction of Tp^Me2Ir(Ph)₂(N₂) (Tp^Me2 = hydrotris(3,5-dimethylpyrazolyl)borate) with di-tert-butyl acetylenedicarboxylate (DTAD) and oxygen is also reported. Our results reveal that the reactions proceed through iridacycle intermediates (detected by NMR) resulting formally from the coupling of one (in the case of 6) or two (for 4b and 5b) molecules of DTAD, with the metal unit "Tp^Me2Ir(C ₆H₄)" derived from the iridium precursor. These intermediates experience very mild and selective oxidation by air to incorporate one (4b and 5b) or three (6) oxygen atoms in the final oxidation products.

Original language	English
Pages (from-to)	2835-2838
Number of pages	4
Journal	Organometallics
Volume	29
Issue number	12
DOIs	https://doi.org/10.1021/om100196h
State	Published - 28 Jun 2010

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title = "Mild oxidation of C-C bonds of benzoiridacycles",

abstract = "We describe herein the formation of two metallacyclic derivatives, 4b and 5b, which contain a coordinated ketone functionality (from an ?-keto ester metallacyclic substituent). An iridafuran, 6, that results from the reaction of TpMe2Ir(Ph)2(N2) (TpMe2 = hydrotris(3,5-dimethylpyrazolyl)borate) with di-tert-butyl acetylenedicarboxylate (DTAD) and oxygen is also reported. Our results reveal that the reactions proceed through iridacycle intermediates (detected by NMR) resulting formally from the coupling of one (in the case of 6) or two (for 4b and 5b) molecules of DTAD, with the metal unit {"}TpMe2Ir(C 6H4){"} derived from the iridium precursor. These intermediates experience very mild and selective oxidation by air to incorporate one (4b and 5b) or three (6) oxygen atoms in the final oxidation products.",

author = "Rosa Padilla and Ver{\'o}nica Salazar and Margarita Paneque and Alvarado-Rodr{\'i}guez, {Jos{\'e} G.} and Joaqu{\'i}n Tamariz and H{\'e}ctor Pacheco-Cuvas and Florencia Vattier",

year = "2010",

month = jun,

day = "28",

doi = "10.1021/om100196h",

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volume = "29",

pages = "2835--2838",

journal = "Organometallics",

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TY - JOUR

T1 - Mild oxidation of C-C bonds of benzoiridacycles

AU - Padilla, Rosa

AU - Salazar, Verónica

AU - Paneque, Margarita

AU - Alvarado-Rodríguez, José G.

AU - Tamariz, Joaquín

AU - Pacheco-Cuvas, Héctor

AU - Vattier, Florencia

PY - 2010/6/28

Y1 - 2010/6/28

N2 - We describe herein the formation of two metallacyclic derivatives, 4b and 5b, which contain a coordinated ketone functionality (from an ?-keto ester metallacyclic substituent). An iridafuran, 6, that results from the reaction of TpMe2Ir(Ph)2(N2) (TpMe2 = hydrotris(3,5-dimethylpyrazolyl)borate) with di-tert-butyl acetylenedicarboxylate (DTAD) and oxygen is also reported. Our results reveal that the reactions proceed through iridacycle intermediates (detected by NMR) resulting formally from the coupling of one (in the case of 6) or two (for 4b and 5b) molecules of DTAD, with the metal unit "TpMe2Ir(C 6H4)" derived from the iridium precursor. These intermediates experience very mild and selective oxidation by air to incorporate one (4b and 5b) or three (6) oxygen atoms in the final oxidation products.

AB - We describe herein the formation of two metallacyclic derivatives, 4b and 5b, which contain a coordinated ketone functionality (from an ?-keto ester metallacyclic substituent). An iridafuran, 6, that results from the reaction of TpMe2Ir(Ph)2(N2) (TpMe2 = hydrotris(3,5-dimethylpyrazolyl)borate) with di-tert-butyl acetylenedicarboxylate (DTAD) and oxygen is also reported. Our results reveal that the reactions proceed through iridacycle intermediates (detected by NMR) resulting formally from the coupling of one (in the case of 6) or two (for 4b and 5b) molecules of DTAD, with the metal unit "TpMe2Ir(C 6H4)" derived from the iridium precursor. These intermediates experience very mild and selective oxidation by air to incorporate one (4b and 5b) or three (6) oxygen atoms in the final oxidation products.

UR - http://www.scopus.com/inward/record.url?scp=77953785042&partnerID=8YFLogxK

U2 - 10.1021/om100196h

DO - 10.1021/om100196h

M3 - Artículo

SN - 0276-7333

VL - 29

SP - 2835

EP - 2838

JO - Organometallics

JF - Organometallics

IS - 12

ER -

Mild oxidation of C-C bonds of benzoiridacycles

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