Issue 28, 2019
From the journal:

Chemical Science

Formation of an imidazoliumyl-substituted [(LC)4P4]4+ tetracation and transition metal mediated fragmentation and insertion reaction (LC = NHC)†

Kai Schwedtmann,a   Jan Haberstroh,‡a   Sven Roediger,‡a   Antonio Bauzá, ORCID logo b   Antonio Frontera, ORCID logo b   Felix Hennersdorf ORCID logo a  and  Jan J. Weigand ORCID logo *a  

* Corresponding authors

a Faculty of Chemistry and Food Chemistry, TU Dresden, Chair of Inorganic Molecular Chemistry, 01062 Dresden, Germany
E-mail: jan.weigand@tu-dresden.de

b Department of Chemistry, Universitat de Illes Balears, 07122 Palma de Mallorca, Spain

Abstract

Tetracationic cyclo-tetraphosphane [(LC)4P4]4+ as triflate salt (3[OTf]4) (LC = 4,5-dimethyl-1,3-diisopropyl-imidazol-2-yl) is obtained in high yield from the reduction of [LCPCl2]+ (4[OTf]) with 1,4-bis(trimethylsilyl)-1,4-dihydropyrazine (6) and represents the first salt of the cationic cyclo-phosphane series with the general formula [LnPn]n+. Theoretical calculations reveal the electrophilic nature of the P atoms within the P4-ring due to the influence of the imidazoliumyl-substituents. Further reduction of 3[OTf]4 with 6 affords the unexpected formation of the notricyclane P7-type cation [(LC)3P7]3+ (9[OTf]3). Selective transition metal mediated [2 + 2]-fragmentation of 34+ is achieved when 3[OTf]4 is reacted with Fe2(CO)9, Pd(PPh3)4 and Pt(PPh3)4 leading to the formation of the dicationic diphosphene complexes [(η2-LCP[double bond, length as m-dash]PLC)Fe(CO)4]2+ (12[OTf]2) and [(η2-LCP[double bond, length as m-dash]PLC)M(PPh3)2]2+ (13[OTf]2 for M = Pd; 14[OTf]2 for M = Pt). In contrast, the reaction of 3[OTf]4 with an excess of AuCl(tht) gives rise to the formation of the five-membered ring complex [((LC)4P4)AuCl2]3+ (15[OTf]3), where the Au(I) atom reductively inserts into a P–P bond of 34+.

Graphical abstract: Formation of an imidazoliumyl-substituted [(LC)4P4]4+ tetracation and transition metal mediated fragmentation and insertion reaction (LC = NHC)

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Article information

DOI
https://doi.org/10.1039/C9SC01701A
Article type
Edge Article
Submitted
07 Apr 2019
Accepted
29 May 2019
First published
30 May 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2019,10, 6868-6875

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Formation of an imidazoliumyl-substituted [(LC)4P4]4+ tetracation and transition metal mediated fragmentation and insertion reaction (LC = NHC)

K. Schwedtmann, J. Haberstroh, S. Roediger, A. Bauzá, A. Frontera, F. Hennersdorf and J. J. Weigand, Chem. Sci., 2019, 10, 6868 DOI: 10.1039/C9SC01701A

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