In:
Angewandte Chemie International Edition, Wiley, Vol. 62, No. 34 ( 2023-08-21)
Abstract:
The synthesis and characterization of ( tBu PBP)Ni(OAc) ( 5 ) by insertion of carbon dioxide into the Ni−C bond of ( tBu PBP)NiMe ( 1 ) is presented. An unexpected CO 2 cleavage process involving the formation of new B−O and Ni−CO bonds leads to the generation of a butterfly‐structured tetra‐nickel cluster ( tBu PBOP) 2 Ni 4 (μ‐CO) 2 ( 6 ). Mechanistic investigation of this reaction indicates a reductive scission of CO 2 by O‐atom transfer to the boron atom via a cooperative nickel‐boron mechanism. The CO 2 activation reaction produces a three‐coordinate ( tBu P 2 BO)Ni‐acyl intermediate ( A ) that leads to a ( tBu P 2 BO)−Ni I complex ( B ) via a likely radical pathway. The Ni I species is trapped by treatment with the radical trap (2,2,6,6‐tetramethylpiperidin‐1‐yl)oxyl (TEMPO) to give ( tBu P 2 BO)Ni II (η 2 ‐TEMPO) ( 7 ). Additionally, 13 C and 1 H NMR spectroscopy analysis using 13 C‐enriched CO 2 provides information about the species involved in the CO 2 activation process.
Type of Medium:
Online Resource
ISSN:
1433-7851
,
1521-3773
DOI:
10.1002/anie.202306315
Language:
English
Publisher:
Wiley
Publication Date:
2023
detail.hit.zdb_id:
2011836-3
detail.hit.zdb_id:
123227-7
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