Journal of Organometallic Chemistry p. 45 - 58 (1996)
Update date:2022-07-29
Topics:
Scherer
Huttner
Buechner
Bakos
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.
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