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Diverse C−C Bond-Forming Reactions of Bis(carbene)platinum(II) Complexes

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/om300733hDOIArticle
http://pubs.acs.org/doi/abs/10.1021/om300733hPublisherArticle
ORCID:
AuthorORCID
Labinger, Jay A.0000-0002-1942-9232
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.
Funders:
Funding AgencyGrant Number
BP MC2 programUNSPECIFIED
NSF Graduate Research FellowshipUNSPECIFIED
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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