Metal-Assisted Opening of Intact P4 Tetrahedra |
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| Authors: | Dr Moritz Modl Dr Sebastian Heinl Dr Gabor Balázs Dr Fuencisla Delgado Calvo Dr Maria Caporali Dr Gabriele Manca Martin Keilwerth Prof Dr Karsten Meyer Prof Dr Maurizio Peruzzini Prof Dr Manfred Scheer |
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| Institution: | 1. Institut für Anorganische Chemie der, Universität Regensburg, 93040 Regensburg, Germany;2. CNR ICCOM, Via Madonna del Piano 10, 50019 Sesto Fiorentino, Italy;3. Department of Chemistry and Pharmacy, Inorganic Chemistry, Friedrich-Alexander-University of Erlangen-Nürnberg (FAU), Egerlandstrasse 1, 91058 Erlangen, Germany |
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| Abstract: | The reactivity of ruthenium and manganese complexes bearing intact white phosphorus in the coordination sphere was investigated towards the low-valent transition-metal species Cp′′′Co] (Cp′′′=η5-C5H2-1,2,4-tBu3) and L0M] (L0=CHCHN(2,6-Me2C6H3)]2; M=Fe, Co). Remarkably, and irrespective of the metal species, the reaction proceeds by the selective cleavage of two P–P edges and the formation of a square-planar cyclo-P4 ligand. The reaction products {CpRu(PPh3)2}{CoCp′′′}(μ,η1:4-P4)]CF3SO3] ( 5 ), {CpBIGMn(CO)2}2{CoCp′′′}(μ,η1:1:4-P4)] ( 6 ) and {CpBIGMn(CO)2}2{ML0}(μ,η1:1:4-P4)] (CpBIG=C5(C6H4nBu)5; L0=CHCHN(2,6-Me2C6H3)]2; M=Fe ( 7 a ), Co ( 7 b )), respectively, were fully characterized by single-crystal X-ray diffraction and spectroscopic methods. The electronic structure of the cyclo-P4 ligand in the complexes 5 – 7 is best described as a π-delocalized P42− system, which is further stabilized by two and three metal moieties, respectively. DFT calculations envisaged a potential intermediate in the reaction to form 5 , in which a quasi-butterfly-shaped P4 moiety bridges the two metals and behaves as an η3-coordinated ligand towards the cobalt center. |
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| Keywords: | cobalt cyclo-P4 ligands diketiminate complexes iron phosphorus |
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