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 language | English |
|---|---|
| Pages (from-to) | 6769-6774 |
| Number of pages | 6 |
| Journal | Inorganic Chemistry |
| Volume | 41 |
| Issue number | 25 |
| DOIs | |
| State | Published - Dec 16 2002 |
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ASJC Scopus subject areas
- Inorganic Chemistry
Cite this
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 journal › Article
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TY - JOUR
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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U2 - 10.1021/ic0204934
DO - 10.1021/ic0204934
M3 - Article
VL - 41
SP - 6769
EP - 6774
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 25
ER -