Comparative Reactivity of Zr– and Pd–Alkyl Complexes with Carbon Dioxide
Structure/reactivity trends and DFT studies reveal mechanistic differences and parallels for the carboxylation of Zr and Pd alkyls. CO2 reacts with Cp2ZrMe(C6D5Cl)+ >104 faster than with Cp2ZrMe2, yielding monoacetate products in both cases. These reactions proceed by insertion mechanisms in whic...
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| Veröffentlicht in: | Organometallics 2013-12, Vol.32 (23), p.6895-6898 |
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| creator | Lau, Ka-Cheong Petro, Benjamin J Bontemps, Sébastien Jordan, Richard F |
| description | Structure/reactivity trends and DFT studies reveal mechanistic differences and parallels for the carboxylation of Zr and Pd alkyls. CO2 reacts with Cp2ZrMe(C6D5Cl)+ >104 faster than with Cp2ZrMe2, yielding monoacetate products in both cases. These reactions proceed by insertion mechanisms in which Zr- - -O interactions activate the CO2. In contrast, CO2 reacts readily with [(PO-iPr)PdMe2]− (PO-iPr– = 2-PiPr2-4-Me-C6H3SO3 –) to yield [(PO-iPr)PdMe(OAc)]− but not with (PO-iPr)PdMe(L) species. Carboxylation of [(PO-iPr)PdMe2]− occurs by direct SE2 attack of CO2 at the Pd–Me trans‑to‑P group, and the nucleophilicity of the Pd–Me group controls the reactivity. However, the SE2 process is accelerated by a Li+- - -OCO interaction when Li+ is present. |
| doi_str_mv | 10.1021/om401082k |
| format | Article |
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CO2 reacts with Cp2ZrMe(C6D5Cl)+ >104 faster than with Cp2ZrMe2, yielding monoacetate products in both cases. These reactions proceed by insertion mechanisms in which Zr- - -O interactions activate the CO2. In contrast, CO2 reacts readily with [(PO-iPr)PdMe2]− (PO-iPr– = 2-PiPr2-4-Me-C6H3SO3 –) to yield [(PO-iPr)PdMe(OAc)]− but not with (PO-iPr)PdMe(L) species. Carboxylation of [(PO-iPr)PdMe2]− occurs by direct SE2 attack of CO2 at the Pd–Me trans‑to‑P group, and the nucleophilicity of the Pd–Me group controls the reactivity. 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CO2 reacts with Cp2ZrMe(C6D5Cl)+ >104 faster than with Cp2ZrMe2, yielding monoacetate products in both cases. These reactions proceed by insertion mechanisms in which Zr- - -O interactions activate the CO2. In contrast, CO2 reacts readily with [(PO-iPr)PdMe2]− (PO-iPr– = 2-PiPr2-4-Me-C6H3SO3 –) to yield [(PO-iPr)PdMe(OAc)]− but not with (PO-iPr)PdMe(L) species. Carboxylation of [(PO-iPr)PdMe2]− occurs by direct SE2 attack of CO2 at the Pd–Me trans‑to‑P group, and the nucleophilicity of the Pd–Me group controls the reactivity. 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CO2 reacts with Cp2ZrMe(C6D5Cl)+ >104 faster than with Cp2ZrMe2, yielding monoacetate products in both cases. These reactions proceed by insertion mechanisms in which Zr- - -O interactions activate the CO2. In contrast, CO2 reacts readily with [(PO-iPr)PdMe2]− (PO-iPr– = 2-PiPr2-4-Me-C6H3SO3 –) to yield [(PO-iPr)PdMe(OAc)]− but not with (PO-iPr)PdMe(L) species. Carboxylation of [(PO-iPr)PdMe2]− occurs by direct SE2 attack of CO2 at the Pd–Me trans‑to‑P group, and the nucleophilicity of the Pd–Me group controls the reactivity. However, the SE2 process is accelerated by a Li+- - -OCO interaction when Li+ is present.</abstract><pub>American Chemical Society</pub><doi>10.1021/om401082k</doi><tpages>4</tpages><orcidid>https://orcid.org/0000-0002-4950-9452</orcidid></addata></record> |
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| title | Comparative Reactivity of Zr– and Pd–Alkyl Complexes with Carbon Dioxide |
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