Transition Metal Complexes with cyclo‐Triphosphorus (η3‐P3) and tetrahedro‐Tetraphosphorus (η1‐P4) Ligands

Salts of 3d, 4d, and 5d metals in the presence of the ligands 1,1,1,-tris(diphenylphosphinomethyl)ethane (triphos) or tris (2-diphenylphosphinoethyl) amine (np3) react with white phosphorus P4 (or yellow As4) to produce several mononuclear sandwich and dinuclear triple-decker sandwich complexes, which contain the unprecedented cyclo-triphosphorus (or cyclo-triarsenic) unit acting as a trihapto-ligand. In these complexes the metal atoms are bonded to the there phosphorus atoms of the phosphane ligand and to the three atoms of the cyclo-P3 or cyclo-As3 unit. The complexes are diamagnetic or have μeff-values corresponding to one or two unpaired electrons. The cyclo-P3 ligand is coordinatively unsaturated as proved by the fact that the mononuclear sandwich compounds may form Lewis-base adducts with electron-acceptor fragments. Reaction of the complexes (np)3M (M = Ni, Pd) with white P4 leads to formation of diamagnetic compounds [(np3)M(η1-P4)], in which the metal atom is bonded to the three phosphorus atoms of the np3-ligand and in addition to one P atom of the intact P4 molecule, which behaves as a monohapto-ligand. This article contains a review of the syntheses and structures of these complexes as well as a unified, albeit qualitative, approach to their bonding and properties.

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