Eine einfache synthese von tripod-liganden H 3CC(CH 2PAr 2) 3: Anwendungsbreite und komplexchemie

Abstract

The reaction of 1,1,1-tris(chlormethyl)ethane H 3CC(CH 2Cl) 3 with Ar 2PH in DMSO as the solvent using KOH/H 2O as the base gives good yields of tripod ligands H 3CC(CH 2PAr 2) 3, 2. Using Ph 2PH as the phosphine component, it is shown that the chloride substituents of H 3CC(CH 2Cl) 3 are exchanged in sequence by the formation of H 3CC(CH 2Cl) 2(CH 2PPh 2), 1a, and H 3CC(CH 2Cl)(CH 2PPh 2) 2, 1b, respectively. The product composition is almost exclusively determined by the applied stoichiometry. The tripod ligands 2 are obtained with Ar = phenyl, 2a, 3-tolyl, 2b, 4-tolyl, 2c, 4- tert-butylphenyl, 2d, 1-naphthyl, 2f, and Ar 2P  dibenzophospholyl, 2e, as Ar 2P groups. Their capability of facial coordination in molybdenum and iron complexes is demonstrated by the characterization of compounds of the type tripod-Mo(CO) 3, 3, and [tripod-Fe(NCCH 3) 3](BF 4) 2, 4. Compounds 1–4 are characterized by the usual spectroscopic and analytical methods as well as by X-ray analysis on selected examples.