Zusammenfassung
The reaction of the P-4 butterfly compound [{Cp'''Fe(CO)(2)}(2)(mu,eta(1:1)-P-4)] (1, Cp''' = (C5H2Bu3)-Bu-t) towards various transition metal complexes is investigated. On the one hand, the reaction of 1 with [(PPh3)Au(tht)][PF6] (tht = tetrahydrothiophene) and [M(CO)(4)(nbd)] (M = Cr, Mo, W; nbd = norbornadiene) yields chelating complexes of the type ...
Zusammenfassung
The reaction of the P-4 butterfly compound [{Cp'''Fe(CO)(2)}(2)(mu,eta(1:1)-P-4)] (1, Cp''' = (C5H2Bu3)-Bu-t) towards various transition metal complexes is investigated. On the one hand, the reaction of 1 with [(PPh3)Au(tht)][PF6] (tht = tetrahydrothiophene) and [M(CO)(4)(nbd)] (M = Cr, Mo, W; nbd = norbornadiene) yields chelating complexes of the type [{Cp'''Fe(CO)(2)}(2)(mu(3),(1:1:1:1)(eta)-P-4){Au(PPh3)}] (2d) and [{Cp'''Fe(CO)(2)}(2)(mu(3),(1:1:1:1)(eta)-P-4){M(CO)(4)}] (2a-c, M = Cr, Mo, W), respectively, bearing intact P-4 butterfly ligands with exceedingly small bite angles (ca. 65 degrees). The reaction of 1 with Ag[PF6] even afforded the spiro complex [{(Cp'''Fe(CO)(2))(2)(mu(3),(1:1:1:1)(eta)-P-4)}(2)Ag][PF6] (3), in which the silver cation is coordinated in a distorted tetrahedral fashion by two P-4 butterfly motifs. On the other hand, the reaction of 1 with the carbonyl containing Lewis acids Fe-2(CO)(9) or Co-2(CO)(8) leads to rearrangement yielding [{Cp'''Fe(CO)(2)}(2){Co(CO)(3)}(2)(mu(4),(2:2:1:1)(eta)-P-4)] (4), incorporating a folded cyclo-P-4 scaffold, and [{Cp'''Fe (CO)(2)}(2)(mu(4),(1:1:1:3)(eta)-P4CO){Fe(CO)(4)}{Fe(CO)(3)}] (5), displaying a tetraphosphole structural motif obtained after carbonyl insertion, respectively. The products are comprehensively characterized by different spectroscopic methods as well as single crystal X-ray diffraction analysis and theoretical calculations.
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