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Theoretical Studies on the Influence of Metallic Cations on Ring Opening of Propylene Oxide Catalyzed by Metal Salen Complexes
  • +1
  • Lei Chen,
  • Hui-Qing Yang,
  • CHENGYU JIN,
  • Zhao-Xu Chen
Lei Chen
Nanjing University
Author Profile
Hui-Qing Yang
Nanjing University
Author Profile
CHENGYU JIN
Nanjing University
Author Profile
Zhao-Xu Chen
Nanjing University
Author Profile

Peer review status:ACCEPTED

29 Feb 2020Submitted to International Journal of Quantum Chemistry
02 Mar 2020Submission Checks Completed
02 Mar 2020Assigned to Editor
03 Mar 2020Reviewer(s) Assigned
24 Mar 2020Review(s) Completed, Editorial Evaluation Pending
24 Mar 2020Editorial Decision: Revise Major
22 May 20201st Revision Received
22 May 2020Submission Checks Completed
22 May 2020Assigned to Editor
03 Jun 2020Reviewer(s) Assigned
03 Jun 2020Review(s) Completed, Editorial Evaluation Pending
03 Jun 2020Editorial Decision: Accept

Abstract

We studied the ring opening of propylene oxide (PO) by salen-M coordinated OH- group [M = Al(Ⅲ), Sc(Ⅲ), Cr(Ⅲ), Mn(Ⅲ), Fe(Ⅲ), Co(Ⅱ), Co(Ⅲ), Ni(Ⅱ), Cu(Ⅱ), Zn(Ⅱ), Ru(Ⅲ) and Rh(Ⅲ)]. The results show that the ring opening energy barriers for M(II) complexes are much lower than those with M(III) complexes in the gas phase, and the barriers correlate linearly with the negative charges on the OH- group, the Fukui function condensed on the OH- group. The nucleophilicity ordering in gas phase can be rationalized by the ratio of formal positive charges/radius of M cations. Solvent effect greatly increases the barriers of M(II) complexes, but slightly changes the results of M(III) ones, making the barriers similar. Analysis indicates that the reaction heats are linearly proportional to the reverse reaction barriers. The relationships established here can be used to estimate the ring opening barriers and to screen epoxide ring opening catalysts.