Photoredox Reactions of cis-Dialkylcobalt(III) Complexes with Benzyl and Allyl Bromides

Shunichi Fukuzumi; Kunio Ishikawa; Toshio Tanaka

doi:10.1021/om00145a020

Photoredox Reactions of cis-Dialkylcobalt(III) Complexes with Benzyl and Allyl Bromides

Shunichi Fukuzumi, Kunio Ishikawa, Toshio Tanaka

Department of Chemistry & Nanoscience

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

19 Scopus citations

Abstract

When the photolysis of an acetonitrile solution of cis-dialkylcobalt(III) complexes cis-[R₂CO(bpy)₂]ClO₄(R = Me and Et; bpy = 2,2^/-bipyridine) was carried out in the presence of benzyl or allyl bromide by using visible light, cis-[R₂Co(bpy)₂]C10₄reacted with approximately three equivalent amounts of benzyl or allyl bromide to yield mainly the homocoupling products 1,2-diphenylethane or 1,5-hexadiene as well as a small amount of the cross-coupling product between the alkyl group of cis-[R₂Co(bpy)₂]C1O₄and the benzyl or allyl group of the bromide. On the other hand, in the photoredox reaction of cis-[(PhCH₂)₂Co(bpy)₂] with benzyl or allyl bromide, cis-[(PhCH₂)₂Co(bpy)₂] reacted with an equivalent amount of benzyl or allyl bromide to yield only the homocoupling product in the case of benzyl bromide or comparable amounts of the homocoupling and cross-coupling products in the case of allyl bromide. Reaction schemes of the photoredox reactions are discussed on the basis of ESR measurements to detect the reactive intermediates as well as the quantum yield measurements.

Original language	English
Pages (from-to)	358-365
Number of pages	8
Journal	Organometallics
Volume	6
Issue number	2
DOIs	https://doi.org/10.1021/om00145a020
State	Published - 1 Feb 1987

Access to Document

10.1021/om00145a020

Cite this

@article{fca910a0937d40aabd4d5ec78abe252b,

title = "Photoredox Reactions of cis-Dialkylcobalt(III) Complexes with Benzyl and Allyl Bromides",

abstract = "When the photolysis of an acetonitrile solution of cis-dialkylcobalt(III) complexes cis-[R2CO(bpy)2]ClO4(R = Me and Et; bpy = 2,2/-bipyridine) was carried out in the presence of benzyl or allyl bromide by using visible light, cis-[R2Co(bpy)2]C104reacted with approximately three equivalent amounts of benzyl or allyl bromide to yield mainly the homocoupling products 1,2-diphenylethane or 1,5-hexadiene as well as a small amount of the cross-coupling product between the alkyl group of cis-[R2Co(bpy)2]C1O4and the benzyl or allyl group of the bromide. On the other hand, in the photoredox reaction of cis-[(PhCH2)2Co(bpy)2] with benzyl or allyl bromide, cis-[(PhCH2)2Co(bpy)2] reacted with an equivalent amount of benzyl or allyl bromide to yield only the homocoupling product in the case of benzyl bromide or comparable amounts of the homocoupling and cross-coupling products in the case of allyl bromide. Reaction schemes of the photoredox reactions are discussed on the basis of ESR measurements to detect the reactive intermediates as well as the quantum yield measurements.",

author = "Shunichi Fukuzumi and Kunio Ishikawa and Toshio Tanaka",

year = "1987",

month = feb,

day = "1",

doi = "10.1021/om00145a020",

language = "English",

volume = "6",

pages = "358--365",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "2",

}

TY - JOUR

T1 - Photoredox Reactions of cis-Dialkylcobalt(III) Complexes with Benzyl and Allyl Bromides

AU - Fukuzumi, Shunichi

AU - Ishikawa, Kunio

AU - Tanaka, Toshio

PY - 1987/2/1

Y1 - 1987/2/1

N2 - When the photolysis of an acetonitrile solution of cis-dialkylcobalt(III) complexes cis-[R2CO(bpy)2]ClO4(R = Me and Et; bpy = 2,2/-bipyridine) was carried out in the presence of benzyl or allyl bromide by using visible light, cis-[R2Co(bpy)2]C104reacted with approximately three equivalent amounts of benzyl or allyl bromide to yield mainly the homocoupling products 1,2-diphenylethane or 1,5-hexadiene as well as a small amount of the cross-coupling product between the alkyl group of cis-[R2Co(bpy)2]C1O4and the benzyl or allyl group of the bromide. On the other hand, in the photoredox reaction of cis-[(PhCH2)2Co(bpy)2] with benzyl or allyl bromide, cis-[(PhCH2)2Co(bpy)2] reacted with an equivalent amount of benzyl or allyl bromide to yield only the homocoupling product in the case of benzyl bromide or comparable amounts of the homocoupling and cross-coupling products in the case of allyl bromide. Reaction schemes of the photoredox reactions are discussed on the basis of ESR measurements to detect the reactive intermediates as well as the quantum yield measurements.

AB - When the photolysis of an acetonitrile solution of cis-dialkylcobalt(III) complexes cis-[R2CO(bpy)2]ClO4(R = Me and Et; bpy = 2,2/-bipyridine) was carried out in the presence of benzyl or allyl bromide by using visible light, cis-[R2Co(bpy)2]C104reacted with approximately three equivalent amounts of benzyl or allyl bromide to yield mainly the homocoupling products 1,2-diphenylethane or 1,5-hexadiene as well as a small amount of the cross-coupling product between the alkyl group of cis-[R2Co(bpy)2]C1O4and the benzyl or allyl group of the bromide. On the other hand, in the photoredox reaction of cis-[(PhCH2)2Co(bpy)2] with benzyl or allyl bromide, cis-[(PhCH2)2Co(bpy)2] reacted with an equivalent amount of benzyl or allyl bromide to yield only the homocoupling product in the case of benzyl bromide or comparable amounts of the homocoupling and cross-coupling products in the case of allyl bromide. Reaction schemes of the photoredox reactions are discussed on the basis of ESR measurements to detect the reactive intermediates as well as the quantum yield measurements.

UR - http://www.scopus.com/inward/record.url?scp=1542309640&partnerID=8YFLogxK

U2 - 10.1021/om00145a020

DO - 10.1021/om00145a020

M3 - Article

AN - SCOPUS:1542309640

SN - 0276-7333

VL - 6

SP - 358

EP - 365

JO - Organometallics

JF - Organometallics

IS - 2

ER -

Photoredox Reactions of cis-Dialkylcobalt(III) Complexes with Benzyl and Allyl Bromides

Abstract

Access to Document

Fingerprint

Cite this