Full Paper

Study of the Transient Reactive Pd(IV) Intermediate in the Pd(OAc)2-Catalyzed Oxidative Coupling Reaction System by Electrospray Ionization Tandem Mass Spectrometry

  1. Wei Zhu,
  2. Haoyang Wang*,
  3. Haihui Peng,
  4. Guosheng Liu,
  5. Yinlong Guo*

Article first published online: 1 MAR 2013

DOI: 10.1002/cjoc.201201167

Issue

Chinese Journal of Chemistry

Chinese Journal of Chemistry

Volume 31, Issue 3, pages 371–376, March, 2013

Additional Information

How to Cite

Zhu, W., Wang, H., Peng, H., Liu, G. and Guo, Y. (2013), Study of the Transient Reactive Pd(IV) Intermediate in the Pd(OAc)2-Catalyzed Oxidative Coupling Reaction System by Electrospray Ionization Tandem Mass Spectrometry. Chin. J. Chem., 31: 371–376. doi: 10.1002/cjoc.201201167

Author Information

  1. Shanghai Mass Spectrometry Center, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China

*Shanghai Mass Spectrometry Center, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China

Publication History

  1. Issue published online: 18 MAR 2013
  2. Article first published online: 1 MAR 2013
  3. Manuscript Accepted: 22 JAN 2013
  4. Manuscript Received: 30 NOV 2012

Funded by

  • the SRF for ROCS of SEM (Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry)
  • NSFC (National Natural Science Foundation of China). Grant Number: 20902104, 21072215, and 21172250
  • the Innovation Method Fund of China. Grant Number: 2011IM030200, 2011IM030400, 2011IM030700

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Keywords:

  • electrospray ionization tandem mass spectrometry (ESI-MS/MS);
  • Pd(IV) transient intermediate;
  • oxidative coupling reaction

Abstract

Pd-catalyzed oxidative coupling reaction was of great importance in the aromatic C[BOND]H activation and the formation of new C[BOND]O and C[BOND]C bonds. Sanford has pioneered practical, directed C[BOND]H activation reactions employing Pd(OAc)2 as catalyst since 2004. However, until now, the speculated reactive Pd(IV) transient intermediates in these reactions have not been isolated or directly detected from reaction solution. Electrospray ionization tandem mass spectrometry (ESI-MS/MS) was used to intercept and characterize the reactive Pd(IV) transient intermediates in the solutions of Pd(OAc)2-catalyzed oxidative coupling reactions. In this study, the Pd(IV) transient intermediates were detected from the solution of Pd(OAc)2-catalyzed oxidative coupling reactions by ESI-MS and the MS/MS of the intercepted Pd(IV) transient intermediate in reaction system was the same with the synthesized authentic Pd(IV) complex. Our ESI-MS(/MS) studies confirmed the presence of Pd(IV) reaction transient intermediates. Most interestingly, the MS/MS of Pd(IV) transient intermediates showed the reductive elimination reactivity to Pd(II) complexes with new C[BOND]O bond formation into product in gas phase, which was consistent with the proposed reactivity of the Pd(IV) transient intermediates in solution.

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