Insertion of Phosphenium Ions into a Bicyclo[1.1.0]Tetraphosphabutane Iron Complex |
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| Authors: | Martin Weber,Gá bor Balá zs,Alexander V. Virovets,Eugenia Peresypkina,Manfred Scheer |
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| Affiliation: | Institute of Inorganic Chemistry, University of Regensburg, Universitätsstrasse 31, 93040 Regensburg, Germany; (M.W.); (G.B.); (A.V.V.); (E.P.) |
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| Abstract: | By reacting [{Cp‴Fe(CO)2}2(µ,η1:1-P4)] (1) with in situ generated phosphenium ions [Ph2P][A] ([A]− = [OTf]− = [O3SCF3]−, [PF6]−), a mixture of two main products of the composition [{Cp‴Fe(CO)2}2(µ,η1:1-P5(C6H5)2)][PF6] (2a and 3a) could be identified by extensive 31P NMR spectroscopic studies at 193 K. Compound 3a was also characterized by X-ray diffraction analysis, showing the rarely observed bicyclo[2.1.0]pentaphosphapentane unit. At room temperature, the novel compound [{Cp‴Fe}(µ,η4:1-P5Ph2){Cp‴(CO)2Fe}][PF6] (4) is formed by decarbonylation. Reacting 1 with in situ generated diphenyl arsenium ions gives short-lived intermediates at 193 K which disproportionate at room temperature into tetraphenyldiarsine and [{Cp‴Fe(CO)2}4(µ4,η1:1:1:1-P8)][OTf]2 (5) containing a tetracyclo[3.3.0.02,7.03,6]octaphosphaoctane ligand. |
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| Keywords: | bicyclo[1.1.0]tetraphosphabutane phosphorus activation arsenium ions phosphenium ions tetracyclo[3.3.0.02 7.03 6]octaphosphaoctane P4 butterfly complex R2P+ insertion |
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