In:
Angewandte Chemie, Wiley, Vol. 136, No. 6 ( 2024-02-05)
Abstract:
Despite the accessibility of numerous transition metal polyphosphido complexes through transition‐metal‐mediated activation of white phosphorus, the targeted functionalization of P n ligands to obtain functional monophosphorus species remains challenging. In this study, we introduce a new [3+1] fragmentation procedure for cyclo ‐P 4 ligands, leading to the discovery of acylcyanophosphanides and ‐phosphines. Treatment of the complex [K(18c‐6)][(Ar*BIAN)Co(η 4 ‐P 4 )] ([K(18c‐6)] 3 , 18c‐6=[18]crown‐6, Ar*=2,6‐dibenzhydryl‐4‐isopropylphenyl, BIAN=1,2‐bis(arylimino)acenaphthene diimine) with acyl chlorides results in the formation of acylated tetraphosphido complexes [(Ar*BIAN)Co(η 4 ‐P 4 C(O)R)] (R= t Bu, Cy, 1‐Ad, Ph; 4 a – d ). Subsequent reactions of 4 a – d with cyanide salts yield acylated cyanophosphanides [RC(O)PCN] − ( 9 a – d − ) and the cyclo ‐P 3 cobaltate anion [(Ar*BIAN)Co(η 3 ‐P 3 )(CN)] − ( 8 − ). Further reactions of 4 a – d with trimethylsilyl cyanide (Me 3 SiCN) and isocyanides provide insight into a plausible mechanism of this [3+1] fragmentation reaction, as these reagents partially displace the P 4 C(O)R ligand from the cobalt center. Several potential intermediates of the [3+1] fragmentation were characterized. Additionally, the introduction of a second acyl substituent was achieved by treating [K(18c‐6)] 9b with CyC(O)Cl, resulting in the first bis(acyl)monocyanophosphine (CyC(O)) 2 PCN ( 10 ).
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.202317170
Language:
English
Publisher:
Wiley
Publication Date:
2024
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505868-5
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1479266-7
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506259-7
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