Article abstract of DOI:10.1016/0022-328X(96)06261-4

The reaction of epichlorohydrine (O-CH₂-CH-CH₂Cl) with lithium - diphenylphosphide (LiP(Ph)₂) yields the alcohol (HOCH(CH₂P(Ph)₂)₂) 1 in a stereochemically controlled reaction. To prove the constitution and coordination ability of 1, the compound has been used to synthesise the homoleptic bisdiphosphine - rhodium complexes trans/cis-[(1)₂Rh¹]B(Ph)₄ 2a,b. The X-ray structure of 2b shows a significant tetrahedral distortion of the planar coordination geometry theoretically favoured for a tetracoordinate metal d⁸ coordination compound. The diphosphino alcohol 1 easily reacts with chiral phosphorchloridites X₂PCl (X₂ = 2 R,4R-2,4-pentanedioxy-(3a); (±)-and R-2,2′-bi-l-naphthoxy-(3b)) to yield chiral-racemic as well as enantiomerically pure mixed donor group tripodal ligands (X₂POCH(CH₂P(Ph)₂)₂) 5a,b containing both phosphite and phosphine donor groups. The identity of these compounds has been proven by ¹H-, ³¹P-and ¹³C-NMR spectroscopy, mass-spectra and microanalysis. The coordination capabilities of these novel tripod ligands are demonstrated by the synthesis and characterisation of the chiral rhodium - cyclooctadiene complexes {[(5a,b)Rh¹(COD)]PF₆} 6a,b, which show the typical hetero-bicyclooctane tripod metal cage of this type of tripod metal template. The rhodium complexes 6a,b are catalysts for the hydrogenation of prochiral olefines. Their activity is not too high and the enantioselectivity is low. The trihapto-coordination of the tripodal ligands is more of an impediment for this type of catalytic transformation.