In:
Angewandte Chemie, Wiley, Vol. 133, No. 17 ( 2021-04-19), p. 9620-9625
Abstract:
We present the η 3 ‐coordination of the 2‐phosphaethynthiolate anion in the complex (PN) 2 La(SCP) ( 2 ) [PN=N‐(2‐(diisopropylphosphanyl)‐4‐methylphenyl)‐2,4,6‐trimethylanilide)]. Structural comparison with dinuclear thiocyanate‐bridged (PN) 2 La(μ‐1,3‐SCN) 2 La(PN) 2 ( 3 ) and azide‐bridged (PN) 2 La(μ‐1,3‐N 3 ) 2 La(PN) 2 ( 4 ) complexes indicates that the [SCP] − coordination mode is mainly governed by electronic, rather than steric factors. Quantum mechanical investigations reveal large contributions of the antibonding π*‐orbital of the [SCP] − ligand to the LUMO of complex 2 , rendering it the ideal precursor for the first functionalization of the [SCP] − anion. Complex 2 was therefore reacted with CAACs which induced a selective rearrangement of the [SCP] − ligand to form the first CAAC stabilized group 15–group 16 fulminate‐type complexes (PN) 2 La{SPC( R CAAC)} ( 5 a,b , R=Ad, Me). A detailed reaction mechanism for the SCP‐to‐SPC isomerization is proposed based on DFT calculations.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v133.17
DOI:
10.1002/ange.202100559
Language:
English
Publisher:
Wiley
Publication Date:
2021
detail.hit.zdb_id:
505868-5
detail.hit.zdb_id:
506609-8
detail.hit.zdb_id:
514305-6
detail.hit.zdb_id:
505872-7
detail.hit.zdb_id:
1479266-7
detail.hit.zdb_id:
505867-3
detail.hit.zdb_id:
506259-7
Bookmarklink