Dinuclear oxidative addition of N-H and S-H bonds at chromium. Reaction of •Cr(CO)3(C5Me5) with {o-(HA)C6H4S-Cr(CO)3 (C5Me5)} (A = S, NH) yielding [η2-o-(μ-A)C6H4S-Cr (C5Me5)]2 and H-Cr(CO)3(C5Me5)

Kengkaj Sukcharoenphon, Telvin D. Ju, Khalil A. Abboud, Carl Hoff

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Abstract

Reaction of the 17-electron radical •Cr(CO)3Cp* (Cp* = C5Me5) with 0.5 equiv of 2-aminophenyl disulfide [(o-H2-NC6H4)2S2] results in rapid oxidative addition to form the initial product (o-H2N)C6H4S-Cr(CO)3Cp*. Addition of a second equivalent of •Cr(CO)3Cp* to this solution results in the formation of H-Cr(CO)3Cp* as well as 1/2[{η2-o-(μ-NH)C6H4S} CrCp*]2. Spectroscopic data show that (o-H2N)C6H4S-Cr(CO)3Cp* loses CO to form {η2-(o-H2N)-C6H4S} Cr(CO)2Cp*. Attack on the N-H bond of the coordinated amine by •Cr(CO)3Cp* provides a reasonable mechanism consistent with the observation that both chelate formation and oxidative addition of the N-H bond are faster under argon than under CO atmosphere. The N-H bonds of uncoordinated aniline do not react with •Cr-(CO)3Cp*. Reaction of the 2 mol of •Cr(CO)3Cp* with 1,2-benzene dithiol [1,2-C6H4(SH)2] yields the initial product (o-HS)C6H4S-Cr(CO)3Cp* and 1 mol of H-Cr(CO)3Cp*. Addition of 1 equiv more of •Cr(CO)3Cp* to this solution also results in the formation of 1 equiv of H-Cr(CO)3Cp*, as well as the dimeric product 1/2[{η2-o-(μ-S)C6H4S}- CrCp*]2. This reaction also occurs more rapidly under Ar than under CO, consistent with intramolecular coordination of the second thiol group prior to oxidative addition. The crystal structures of [{η2-o-(μ-NH)C6H4S} CrCp*]2 and [{η2-o-(μ-S)C6H4S} CrCp*]2 are reported.

Original languageEnglish
Pages (from-to)6769-6774
Number of pages6
JournalInorganic Chemistry
Volume41
Issue number25
DOIs
StatePublished - Dec 16 2002

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Chromium
Carbon Monoxide
chromium
thiols
products
disulfides
aniline
chelates
attack
amines
benzene
argon
atmospheres
crystal structure
electrons
Argon
Benzene
Sulfhydryl Compounds
Disulfides
Amines

ASJC Scopus subject areas

  • Inorganic Chemistry

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Dinuclear oxidative addition of N-H and S-H bonds at chromium. Reaction of •Cr(CO)3(C5Me5) with {o-(HA)C6H4S-Cr(CO)3 (C5Me5)} (A = S, NH) yielding [η2-o-(μ-A)C6H4S-Cr (C5Me5)]2 and H-Cr(CO)3(C5Me5). / Sukcharoenphon, Kengkaj; Ju, Telvin D.; Abboud, Khalil A.; Hoff, Carl.

In: Inorganic Chemistry, Vol. 41, No. 25, 16.12.2002, p. 6769-6774.

Research output: Contribution to journalArticle

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title = "Dinuclear oxidative addition of N-H and S-H bonds at chromium. Reaction of •Cr(CO)3(C5Me5) with {o-(HA)C6H4S-Cr(CO)3 (C5Me5)} (A = S, NH) yielding [η2-o-(μ-A)C6H4S-Cr (C5Me5)]2 and H-Cr(CO)3(C5Me5)",
abstract = "Reaction of the 17-electron radical •Cr(CO)3Cp* (Cp* = C5Me5) with 0.5 equiv of 2-aminophenyl disulfide [(o-H2-NC6H4)2S2] results in rapid oxidative addition to form the initial product (o-H2N)C6H4S-Cr(CO)3Cp*. Addition of a second equivalent of •Cr(CO)3Cp* to this solution results in the formation of H-Cr(CO)3Cp* as well as 1/2[{η2-o-(μ-NH)C6H4S} CrCp*]2. Spectroscopic data show that (o-H2N)C6H4S-Cr(CO)3Cp* loses CO to form {η2-(o-H2N)-C6H4S} Cr(CO)2Cp*. Attack on the N-H bond of the coordinated amine by •Cr(CO)3Cp* provides a reasonable mechanism consistent with the observation that both chelate formation and oxidative addition of the N-H bond are faster under argon than under CO atmosphere. The N-H bonds of uncoordinated aniline do not react with •Cr-(CO)3Cp*. Reaction of the 2 mol of •Cr(CO)3Cp* with 1,2-benzene dithiol [1,2-C6H4(SH)2] yields the initial product (o-HS)C6H4S-Cr(CO)3Cp* and 1 mol of H-Cr(CO)3Cp*. Addition of 1 equiv more of •Cr(CO)3Cp* to this solution also results in the formation of 1 equiv of H-Cr(CO)3Cp*, as well as the dimeric product 1/2[{η2-o-(μ-S)C6H4S}- CrCp*]2. This reaction also occurs more rapidly under Ar than under CO, consistent with intramolecular coordination of the second thiol group prior to oxidative addition. The crystal structures of [{η2-o-(μ-NH)C6H4S} CrCp*]2 and [{η2-o-(μ-S)C6H4S} CrCp*]2 are reported.",
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T1 - Dinuclear oxidative addition of N-H and S-H bonds at chromium. Reaction of •Cr(CO)3(C5Me5) with {o-(HA)C6H4S-Cr(CO)3 (C5Me5)} (A = S, NH) yielding [η2-o-(μ-A)C6H4S-Cr (C5Me5)]2 and H-Cr(CO)3(C5Me5)

AU - Sukcharoenphon, Kengkaj

AU - Ju, Telvin D.

AU - Abboud, Khalil A.

AU - Hoff, Carl

PY - 2002/12/16

Y1 - 2002/12/16

N2 - Reaction of the 17-electron radical •Cr(CO)3Cp* (Cp* = C5Me5) with 0.5 equiv of 2-aminophenyl disulfide [(o-H2-NC6H4)2S2] results in rapid oxidative addition to form the initial product (o-H2N)C6H4S-Cr(CO)3Cp*. Addition of a second equivalent of •Cr(CO)3Cp* to this solution results in the formation of H-Cr(CO)3Cp* as well as 1/2[{η2-o-(μ-NH)C6H4S} CrCp*]2. Spectroscopic data show that (o-H2N)C6H4S-Cr(CO)3Cp* loses CO to form {η2-(o-H2N)-C6H4S} Cr(CO)2Cp*. Attack on the N-H bond of the coordinated amine by •Cr(CO)3Cp* provides a reasonable mechanism consistent with the observation that both chelate formation and oxidative addition of the N-H bond are faster under argon than under CO atmosphere. The N-H bonds of uncoordinated aniline do not react with •Cr-(CO)3Cp*. Reaction of the 2 mol of •Cr(CO)3Cp* with 1,2-benzene dithiol [1,2-C6H4(SH)2] yields the initial product (o-HS)C6H4S-Cr(CO)3Cp* and 1 mol of H-Cr(CO)3Cp*. Addition of 1 equiv more of •Cr(CO)3Cp* to this solution also results in the formation of 1 equiv of H-Cr(CO)3Cp*, as well as the dimeric product 1/2[{η2-o-(μ-S)C6H4S}- CrCp*]2. This reaction also occurs more rapidly under Ar than under CO, consistent with intramolecular coordination of the second thiol group prior to oxidative addition. The crystal structures of [{η2-o-(μ-NH)C6H4S} CrCp*]2 and [{η2-o-(μ-S)C6H4S} CrCp*]2 are reported.

AB - Reaction of the 17-electron radical •Cr(CO)3Cp* (Cp* = C5Me5) with 0.5 equiv of 2-aminophenyl disulfide [(o-H2-NC6H4)2S2] results in rapid oxidative addition to form the initial product (o-H2N)C6H4S-Cr(CO)3Cp*. Addition of a second equivalent of •Cr(CO)3Cp* to this solution results in the formation of H-Cr(CO)3Cp* as well as 1/2[{η2-o-(μ-NH)C6H4S} CrCp*]2. Spectroscopic data show that (o-H2N)C6H4S-Cr(CO)3Cp* loses CO to form {η2-(o-H2N)-C6H4S} Cr(CO)2Cp*. Attack on the N-H bond of the coordinated amine by •Cr(CO)3Cp* provides a reasonable mechanism consistent with the observation that both chelate formation and oxidative addition of the N-H bond are faster under argon than under CO atmosphere. The N-H bonds of uncoordinated aniline do not react with •Cr-(CO)3Cp*. Reaction of the 2 mol of •Cr(CO)3Cp* with 1,2-benzene dithiol [1,2-C6H4(SH)2] yields the initial product (o-HS)C6H4S-Cr(CO)3Cp* and 1 mol of H-Cr(CO)3Cp*. Addition of 1 equiv more of •Cr(CO)3Cp* to this solution also results in the formation of 1 equiv of H-Cr(CO)3Cp*, as well as the dimeric product 1/2[{η2-o-(μ-S)C6H4S}- CrCp*]2. This reaction also occurs more rapidly under Ar than under CO, consistent with intramolecular coordination of the second thiol group prior to oxidative addition. The crystal structures of [{η2-o-(μ-NH)C6H4S} CrCp*]2 and [{η2-o-(μ-S)C6H4S} CrCp*]2 are reported.

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