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 (US) |
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Pages (from-to) | 6769-6774 |
Number of pages | 6 |
Journal | Inorganic Chemistry |
Volume | 41 |
Issue number | 25 |
DOIs | |
State | Published - Dec 16 2002 |
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry