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Gas-Phase Formation of Grignard-type Organolanthanide(III) Ions RLnCl3-: the Influences of Lanthanide Center and Hydrocarbyl Group
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  • Meixian Yang,
  • Zhixin Xiong,
  • Yangjuan Li,
  • xiuting Chen,
  • Wei Zhou
Meixian Yang
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Zhixin Xiong
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Yangjuan Li
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xiuting Chen

Corresponding Author:chenxiuting@sinap.ac.cn

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Wei Zhou
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Rationale: The fundamental understanding of Grignard-type organolanthanides(III) is still in its infancy. Decarboxylation of metal carboxylate ions is a powerful method to obtain organometallic ions which are well suited for gas-phase investigation by using ESI-MS in combination with DFT calculations. Methods: (RCO2)LnCl3- (R = CH3, Ln = La-Lu except Pm; Ln = La, R = CH3CH2, CH2CH, CHC, C6H5 and C6H11) ions were produced via ESI of LnCl3 and RCO2H/RCO2Na in methanol. Collision-induced dissociation (CID) was employed to examine whether RLnCl3- can be obtained via decarboxylation of (RCO2)LnCl3-. With the aid of DFT calculations, the influences of Ln and R on the formation of RLnCl3- can be uncovered. Results: When R was fixed as methyl, CID of (CH3CO2)LnCl3- (Ln = La-Lu except Pm) all gave (CH3)LnCl3- and LnCl3·- with a variation in the relative intensity ratio of (CH3)LnCl3-/LnCl3·-. The trend is following as (CH3)EuCl3-/EuCl3·- < (CH3)YbCl3-/YbCl3·- ≈ (CH3)SmCl3-/SmCl3·- < other (CH3)LnCl3-/LnCl3·-, which generally complies with the trend of Ln(III)/Ln(II) reduction potentials. When Ln was fixed as La and R groups were varied as CH3CH2, CH2CH, CHC, C6H5 and C6H11, the fragmentation behaviors of these (RCO2)LaCl3- are diverse. Except for (C6H11CO2)LaCl3-, the rest four (RCO2)LaCl3- ions all underwent decarboxylation to give RLaCl3-. The relative intensities of RLaCl3- compared to (RCO2)LaCl3- decrease as follow: CHC > CH2CH > C6H5 > CH3 > CH3CH2 >> C6H11 (not visible). Conclusion: A series of Grignard-type organolanthanide(III) ions RLnCl3- (R = CH3, Ln = La-Lu except Pm; Ln = La, R = CH3CH2, CH2CH, CHC and C6H5) were generated from (RCO2)LnCl3- via CO2 loss while (C6H5)LaCl3- not. The experimental and theoretical results suggest that the reduction potentials of Ln(III)/Ln(II) couples as well as the bulkiness and hybridization of hydrocarbyl groups play crucial roles in promoting or limiting the formation of RLnCl3- via decarboxylation.
12 Jan 2023Submitted to Rapid Communications in Mass Spectrometry
13 Jan 2023Submission Checks Completed
13 Jan 2023Assigned to Editor
13 Jan 2023Review(s) Completed, Editorial Evaluation Pending
13 Jan 2023Reviewer(s) Assigned
10 Mar 2023Editorial Decision: Revise Major
17 Mar 20231st Revision Received
17 Mar 2023Submission Checks Completed
17 Mar 2023Assigned to Editor
17 Mar 2023Review(s) Completed, Editorial Evaluation Pending
20 Mar 2023Editorial Decision: Accept