In:
European Journal of Inorganic Chemistry, Wiley, Vol. 2021, No. 38 ( 2021-10-14), p. 4030-4041
Abstract:
The C=C bond in selected N ‐alkyl/aryl‐maleimides RN(C(O)CH) 2 (R=Me, t Bu, Ph) is activated by organopnictogen(I) compounds producing bridged bicyclic [2.2.1] products exhibiting both endo and exo orientations. This is achieved by a synergic element‐ligand cooperation, thereby resembling a hetero‐Diels‐Alder reaction. A wide range of pnictogen(I) complexes is considered in this study including the bis(aldiminine) pincer compounds ArE ( 1 ) (Ar=2,6‐(R'N=CH) 2 C 6 H 3 , R’= t Bu, E=P (P‐ 1 ), As (As‐ 1 ), Sb (Sb‐ 1 ), Bi (Bi‐ 1 ) or R’=Dmp, E=P (P‐ 1’ ), As (As‐ 1’ ), Sb (Sb ‐1’ ), where Dmp=2,6‐Me 2 C 6 H 3 ) and the C,N ‐coordinated compounds Ar'E ( 2 ) (Ar’=2‐(DippN=CH)C 6 H 4 , E=P (P‐ 2 ), As (As‐ 2 ), where Dipp=2,6‐ i Pr 2 C 6 H 3 ). On this set of compounds, the reversibility of C=C bond activation was examined mainly by means of the 1 H variable temperature (VT) NMR spectroscopy and this study revealed trends showing a dependence both on the E atom and on the structure of the ligand. The structure of the addition products was elucidated by multinuclear NMR and single‐crystal X‐ray diffraction analysis. The whole study is accompanied by a theoretical survey targeting decisive factors for the C=C bond activation and a preference for endo / exo forms by the particular pnictogen(I) compound.
Type of Medium:
Online Resource
ISSN:
1434-1948
,
1099-0682
DOI:
10.1002/ejic.v2021.38
DOI:
10.1002/ejic.202100648
Language:
English
Publisher:
Wiley
Publication Date:
2021
detail.hit.zdb_id:
1475009-0
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