Photochemical reaction of CpIr(CO)2 with C6F 5X (X = CN, F): Formation of diiridium(II) complexes

Kar Hang Garvin Mak; Pek Ke Chan; Wai Yip Fan; Rakesh Ganguly; Weng Kee Leong

doi:10.1021/om301055h

Photochemical reaction of CpIr(CO)₂ with C₆F ₅X (X = CN, F): Formation of diiridium(II) complexes

Kar Hang Garvin Mak, Pek Ke Chan, Wai Yip Fan^*, Rakesh Ganguly, Weng Kee Leong

^*Corresponding author for this work

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

15 Citations (Scopus)

Abstract

Visible light irradiation of CpIr(CO)₂ (1) in pentafluorobenzontrile resulted in the formation of the two isomeric diiridium(II) complexes [CpIr(μ-CO)(C₆F₄CN)] ₂ (3) and [CpIr(CO)(C₆F₄CN)]₂ (4), while the analogous reaction of 1 in hexafluorobenzene to give [CpIr(μ-CO)(C₆F₅)]₂ (3a) required UV irradiation. Complex 4 isomerizes to 3 under visible light irradiation. A reaction pathway to 4 involving aromatic nucleophilic substitution has been proposed on the basis of experimental and computational data. The isomerization of 4 to 3 is believed to proceed via a radical species resulting from homolytic fission of the Ir-Ir bond.

Original language	English
Pages (from-to)	1053-1059
Number of pages	7
Journal	Organometallics
Volume	32
Issue number	4
DOIs	https://doi.org/10.1021/om301055h
Publication status	Published - Feb 25 2013
Externally published	Yes

ASJC Scopus Subject Areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Photochemical reaction of CpIr(CO)2 with C6F 5X (X = CN, F): Formation of diiridium(II) complexes",

abstract = "Visible light irradiation of CpIr(CO)2 (1) in pentafluorobenzontrile resulted in the formation of the two isomeric diiridium(II) complexes [CpIr(μ-CO)(C6F4CN)] 2 (3) and [CpIr(CO)(C6F4CN)]2 (4), while the analogous reaction of 1 in hexafluorobenzene to give [CpIr(μ-CO)(C6F5)]2 (3a) required UV irradiation. Complex 4 isomerizes to 3 under visible light irradiation. A reaction pathway to 4 involving aromatic nucleophilic substitution has been proposed on the basis of experimental and computational data. The isomerization of 4 to 3 is believed to proceed via a radical species resulting from homolytic fission of the Ir-Ir bond.",

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T1 - Photochemical reaction of CpIr(CO)2 with C6F 5X (X = CN, F)

T2 - Formation of diiridium(II) complexes

AU - Mak, Kar Hang Garvin

AU - Chan, Pek Ke

AU - Fan, Wai Yip

AU - Ganguly, Rakesh

AU - Leong, Weng Kee

PY - 2013/2/25

Y1 - 2013/2/25

N2 - Visible light irradiation of CpIr(CO)2 (1) in pentafluorobenzontrile resulted in the formation of the two isomeric diiridium(II) complexes [CpIr(μ-CO)(C6F4CN)] 2 (3) and [CpIr(CO)(C6F4CN)]2 (4), while the analogous reaction of 1 in hexafluorobenzene to give [CpIr(μ-CO)(C6F5)]2 (3a) required UV irradiation. Complex 4 isomerizes to 3 under visible light irradiation. A reaction pathway to 4 involving aromatic nucleophilic substitution has been proposed on the basis of experimental and computational data. The isomerization of 4 to 3 is believed to proceed via a radical species resulting from homolytic fission of the Ir-Ir bond.

AB - Visible light irradiation of CpIr(CO)2 (1) in pentafluorobenzontrile resulted in the formation of the two isomeric diiridium(II) complexes [CpIr(μ-CO)(C6F4CN)] 2 (3) and [CpIr(CO)(C6F4CN)]2 (4), while the analogous reaction of 1 in hexafluorobenzene to give [CpIr(μ-CO)(C6F5)]2 (3a) required UV irradiation. Complex 4 isomerizes to 3 under visible light irradiation. A reaction pathway to 4 involving aromatic nucleophilic substitution has been proposed on the basis of experimental and computational data. The isomerization of 4 to 3 is believed to proceed via a radical species resulting from homolytic fission of the Ir-Ir bond.

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Photochemical reaction of CpIr(CO)₂ with C₆F ₅X (X = CN, F): Formation of diiridium(II) complexes

Abstract

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