Synthesis and oxidation of chiral rhenium phosphine methyl complexes of the formula (η5-C5Me5)Re(NO)(PR3)(CH3): In search of radical cations with enhanced kinetic stabilities

Wayne E. Meyer; Angelo J. Amoroso; Monika Jaeger; Jean Le Bras; Wing Tak Wong; J. A. Gladysz

doi:10.1016/S0022-328X(00)00528-3

Synthesis and oxidation of chiral rhenium phosphine methyl complexes of the formula (η⁵-C₅Me₅)Re(NO)(PR₃)(CH₃): In search of radical cations with enhanced kinetic stabilities

Wayne E. Meyer, Angelo J. Amoroso, Monika Jaeger, Jean Le Bras, Wing Tak Wong, J. A. Gladysz

Research output: Journal article publication › Journal article › Academic research › peer-review

14 Citations (Scopus)

Abstract

Reactions of racemic [(η5-C5Me5)Re(NO)(NCCH3)(CO)]+BF-4and phosphines PR3(R = C6H5a; 4-C6H4CH3b; 4-C6H4-t-C4H9c; 4-C6H4C6H5d; 4-C6H4OCH3e; C-C6H11f) give the phosphine carbonyl complexes [(η5-C5Me5)Re(NO)(PR3)(CO)]+BF-4(5a-5f+BF-4; 55-95%). These are treated with LiEt3BH and then BH3·THF to give the phosphine methyl complexes (η5-C5Me5)Re(NO)(PR3)(CH3) (2a-2f, 50-86%). Cyclic voltammetry shows that the new compounds 2b-2f undergo chemically reversible one-electron oxidations that are thermodynamically more favorable than that of 2a (ΔE○ = 0.07, 0.07, 0.01, 0.09, 0.22 V; CH2Cl2). The radical cations 2•+X-can be generated with Ag+X-or (η5-C5H5)2Fe•+X-(X-= PF-6, SbF-6), as evidenced by IR and ESR spectra, but are labile and efforts to isolate pure salts fail. Reaction of 2a and TCNE give (η5-C5Me5)Re(NO)(η2-TCNE)(CH3), which is crystallographically characterized and proposed to form by initial electron transfer followed by radical chain substitution.

Original language	English
Pages (from-to)	44-53
Number of pages	10
Journal	Journal of Organometallic Chemistry
Volume	616
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(00)00528-3
Publication status	Published - 15 Dec 2000
Externally published	Yes

Keywords

Cyclic voltammetry
ESR
Radical cations
Rhenium
TCNE

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

More information

10.1016/S0022-328X(00)00528-3

Cite this

@article{9414ff8581b842459a38a06a39a26eca,

title = "Synthesis and oxidation of chiral rhenium phosphine methyl complexes of the formula (η5-C5Me5)Re(NO)(PR3)(CH3): In search of radical cations with enhanced kinetic stabilities",

abstract = "Reactions of racemic [(η5-C5Me5)Re(NO)(NCCH3)(CO)]+BF-4and phosphines PR3(R = C6H5a; 4-C6H4CH3b; 4-C6H4-t-C4H9c; 4-C6H4C6H5d; 4-C6H4OCH3e; C-C6H11f) give the phosphine carbonyl complexes [(η5-C5Me5)Re(NO)(PR3)(CO)]+BF-4(5a-5f+BF-4; 55-95%). These are treated with LiEt3BH and then BH3·THF to give the phosphine methyl complexes (η5-C5Me5)Re(NO)(PR3)(CH3) (2a-2f, 50-86%). Cyclic voltammetry shows that the new compounds 2b-2f undergo chemically reversible one-electron oxidations that are thermodynamically more favorable than that of 2a (ΔE○ = 0.07, 0.07, 0.01, 0.09, 0.22 V; CH2Cl2). The radical cations 2•+X-can be generated with Ag+X-or (η5-C5H5)2Fe•+X-(X-= PF-6, SbF-6), as evidenced by IR and ESR spectra, but are labile and efforts to isolate pure salts fail. Reaction of 2a and TCNE give (η5-C5Me5)Re(NO)(η2-TCNE)(CH3), which is crystallographically characterized and proposed to form by initial electron transfer followed by radical chain substitution.",

keywords = "Cyclic voltammetry, ESR, Radical cations, Rhenium, TCNE",

author = "Meyer, {Wayne E.} and Amoroso, {Angelo J.} and Monika Jaeger and {Le Bras}, Jean and Wong, {Wing Tak} and Gladysz, {J. A.}",

year = "2000",

month = dec,

day = "15",

doi = "10.1016/S0022-328X(00)00528-3",

language = "English",

volume = "616",

pages = "44--53",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier B.V.",

number = "1-2",

}

Synthesis and oxidation of chiral rhenium phosphine methyl complexes of the formula (η⁵-C₅Me₅)Re(NO)(PR₃)(CH₃): In search of radical cations with enhanced kinetic stabilities. / Meyer, Wayne E.; Amoroso, Angelo J.; Jaeger, Monika et al.
In: Journal of Organometallic Chemistry, Vol. 616, No. 1-2, 15.12.2000, p. 44-53.

Research output: Journal article publication › Journal article › Academic research › peer-review

TY - JOUR

T1 - Synthesis and oxidation of chiral rhenium phosphine methyl complexes of the formula (η5-C5Me5)Re(NO)(PR3)(CH3): In search of radical cations with enhanced kinetic stabilities

AU - Meyer, Wayne E.

AU - Amoroso, Angelo J.

AU - Jaeger, Monika

AU - Le Bras, Jean

AU - Wong, Wing Tak

AU - Gladysz, J. A.

PY - 2000/12/15

Y1 - 2000/12/15

N2 - Reactions of racemic [(η5-C5Me5)Re(NO)(NCCH3)(CO)]+BF-4and phosphines PR3(R = C6H5a; 4-C6H4CH3b; 4-C6H4-t-C4H9c; 4-C6H4C6H5d; 4-C6H4OCH3e; C-C6H11f) give the phosphine carbonyl complexes [(η5-C5Me5)Re(NO)(PR3)(CO)]+BF-4(5a-5f+BF-4; 55-95%). These are treated with LiEt3BH and then BH3·THF to give the phosphine methyl complexes (η5-C5Me5)Re(NO)(PR3)(CH3) (2a-2f, 50-86%). Cyclic voltammetry shows that the new compounds 2b-2f undergo chemically reversible one-electron oxidations that are thermodynamically more favorable than that of 2a (ΔE○ = 0.07, 0.07, 0.01, 0.09, 0.22 V; CH2Cl2). The radical cations 2•+X-can be generated with Ag+X-or (η5-C5H5)2Fe•+X-(X-= PF-6, SbF-6), as evidenced by IR and ESR spectra, but are labile and efforts to isolate pure salts fail. Reaction of 2a and TCNE give (η5-C5Me5)Re(NO)(η2-TCNE)(CH3), which is crystallographically characterized and proposed to form by initial electron transfer followed by radical chain substitution.

AB - Reactions of racemic [(η5-C5Me5)Re(NO)(NCCH3)(CO)]+BF-4and phosphines PR3(R = C6H5a; 4-C6H4CH3b; 4-C6H4-t-C4H9c; 4-C6H4C6H5d; 4-C6H4OCH3e; C-C6H11f) give the phosphine carbonyl complexes [(η5-C5Me5)Re(NO)(PR3)(CO)]+BF-4(5a-5f+BF-4; 55-95%). These are treated with LiEt3BH and then BH3·THF to give the phosphine methyl complexes (η5-C5Me5)Re(NO)(PR3)(CH3) (2a-2f, 50-86%). Cyclic voltammetry shows that the new compounds 2b-2f undergo chemically reversible one-electron oxidations that are thermodynamically more favorable than that of 2a (ΔE○ = 0.07, 0.07, 0.01, 0.09, 0.22 V; CH2Cl2). The radical cations 2•+X-can be generated with Ag+X-or (η5-C5H5)2Fe•+X-(X-= PF-6, SbF-6), as evidenced by IR and ESR spectra, but are labile and efforts to isolate pure salts fail. Reaction of 2a and TCNE give (η5-C5Me5)Re(NO)(η2-TCNE)(CH3), which is crystallographically characterized and proposed to form by initial electron transfer followed by radical chain substitution.

KW - Cyclic voltammetry

KW - ESR

KW - Radical cations

KW - Rhenium

KW - TCNE

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U2 - 10.1016/S0022-328X(00)00528-3

DO - 10.1016/S0022-328X(00)00528-3

M3 - Journal article

SN - 0022-328X

VL - 616

SP - 44

EP - 53

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1-2

ER -