Klet, Rachel C. and Labinger, Jay A. and Bercaw, John E. (2012) Diverse C−C Bond-Forming Reactions of Bis(carbene)platinum(II) Complexes. Organometallics, 31 (18). pp. 6652-6657. ISSN 0276-7333. doi:10.1021/om300733h. https://resolver.caltech.edu/CaltechAUTHORS:20121114-105428991
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Abstract
The platinum(0) complex Pt(PPh_3)_4 catalyzes coupling of the carbene ligands of (CO)_5Cr{C(OMe)(p-MeOC_6H_4)} (1). The stable bis(carbene)platinum(II) complexes Cl_2Pt{C(OMe)(Me)}_2 (3), Br_2Pt{C(OMe)(Me)}_2 (4), and Cl_2Pt{C(O^iPr)(Me)}_2 (5) can be induced to undergo C–C coupling reactions by several means. Reduction of 3–5 to platinum(0) with cobaltocene results in formation of internal olefins, (E/Z)-2,3-dimethoxybut-2-ene (6) or (E/Z)-2,3-diisopropoxybut-2-ene (7). Reaction of 3–5 with PPh3 yields terminal olefins, 2,3-dimethoxybut-1-ene (13) or 2,3-diisopropoxybut-1-ene (15), along with Cl_2Pt(PPh_3)_2 (12) or Br_2Pt(PPh_3)_2 (14). In contrast, addition of pyridine to 3–5 does not effect C–C coupling; instead, the acyl complexes cis-Cl(py)Pt(COMe){C(OMe)(Me)} (8), cis-Br(py)Pt(COMe){C(OMe)(Me)} (9), and cis-Cl(py)Pt(COMe){C(O^iPr)(Me)} (10) are obtained, with concomitant formation of alkyl halide. Possible mechanistic pathways for C–C bond formation are discussed, as well as explanations for the different reactivities observed for pyridine and PPh_3.
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| Additional Information: | © 2012 American Chemical Society. Received: August 1, 2012. Publication Date (Web): August 31, 2012. This work was generously funded by BP through the Methane Conversion Cooperative (MC2) program. An NSF-GRF to R.C.K. is gratefully acknowledged. We thank Dr. David VanderVelde for assistance with NMR experiments. R.C.K. is grateful to Prof. Alexander J. M. Miller and Prof. Theodor Agapie for useful discussions. The authors declare no competing financial interest. | |||||||||
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| Issue or Number: | 18 | |||||||||
| DOI: | 10.1021/om300733h | |||||||||
| Record Number: | CaltechAUTHORS:20121114-105428991 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20121114-105428991 | |||||||||
| Official Citation: | Diverse C–C Bond-Forming Reactions of Bis(carbene)platinum(II) Complexes Rachel C. Klet, Jay A. Labinger, and John E. Bercaw Organometallics 2012 31 (18), 6652-6657 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 35457 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Ruth Sustaita | |||||||||
| Deposited On: | 14 Nov 2012 19:30 | |||||||||
| Last Modified: | 09 Nov 2021 23:15 |
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