Zur Transformation des P4‐Tetraeders durch Ni‐Komplexe

Abstract

The Transformation Pathway of the P4 Tetrahedron by Ni ComplexesThe thermal reaction of [Cp*NiCO]2 with white phosphorus in the presence of [Cr(CO)5(thf)] at 70°C produces the bent cyclo‐P4 ligand complex 4 and the Ni2P4 prismane 5. However under photochemical conditions additional products such as cyclo‐P3 complexes 6 and the Ni2P2 tetrahedrane 7 are also formed. 4 and 5 were characterized by NMR, IR, and mass spectroscopy as well as by X‐ray structure analysis. The structures of these products and the experimentals verification of the conversion of 4 into 5 or into 6 and 7 as well as the cubane analog 12 gives evidence for a transformation pathway starting from P4 tetrahedron via a possible bicyclotetraphosphane intermediate to give the bent P4 complex 4. From 4 several pathways are possible; the main route is to form the Ni2P4 prismane 5. Photochemically a P3/P1 fragmentation also occurs, albeit in low yield, to give 5 and 6.