60219-90-1Relevant academic research and scientific papers
Synthesis and coordination chemistry of chelate ligands containing cyclopentadienyl, indenyl and fluorenyl donors - Diastereoselectivity and NMR structure analysis
Vogelgesang, Joachim,Frick, Axel,Huttner, Gottfried,Kircher, Peter
, p. 949 - 971 (2007/10/03)
The functionalised oxetane O(CH2)2C(CH2Br)(CH2OMs) (1) is transformed into tripod ligands ROCH2C(CH2PPh2)(CH2PR′ 2)(CH2Cp#) (R = H, SiMe3; R′ = Ph, Et; Cp# = indenyl, fluorenyl) (4) in a few steps. Epichlorohydrin O(CH2)CH(CH2Cl) (5) allows for diastereoselective one-pot syntheses of the Cp-functionalised chelate ligands (Cp#CH2)C(H)OH(CH2PPh2) (Cp# = Cp, indenyl, fluorenyl) (6). The SiMe3-protected derivatives of these ligands react with RuCl2(PPh3)3 to produce {Me3SiOCH(CH2-η1PPh2)(CH 2-η5-Cp#)Ru(PPh3)(Cl)} (Cp# = Cp, indenyl) (15) with high diastereoselective preference. With the same starting material, tripod ligands 4 form Me3SiOCH2C(CH2-η1PPh 2)(CH2-η1PR2)(CH2 -η5-Indenyl)RuCl (R = Ph, Et) (16). As shown by complete NMR spectroscopy based structure analyses (DG methods) of 16, the formation of 16 (R = Et) is diastereoselective. The only diastereomer which is observed is the one in which the PEt2 donor and the phenylene part of the indenyl ligand are juxtaposed. In addition to quantitative NMR spectroscopy structure analyses, traditional analytical techniques, including X-ray analyses, were used to confirm the results.
Chiral Tripodal Ligands Bearing a Phosphite Donor Group: Synthesis and Coordination Chemistry
Scherer, Johannes,Huttner, Gottfried,Buechner, Michael
, p. 697 - 713 (2007/10/03)
The mechanism of the reaction of epichlorohydrine (O-CH2-CH-CH2Cl) (I) with lithium phosphides is analysed. A neighbouring-group mechanism has been found to be the essential driving force in this reaction, Monophosphanyl alcohols such as HOCH(CH2P(Ph)2)(CH2Cl) (2) and epoxides (Ph)2PCH2-CH-CH2-O (3) are characterized as intermediates. The mechanism leads to a rapid one-pot method for the synthesis of chiral racemic as well as enantiomencally pure bis(phosphanyl) alcohols HOCH(CH2PR2){CH2PR2) (4). The resulting bis(phosphanyl) alcohols 4 react easily with X2PCl (X= Cl; Ph; or X2= 1,2-ethanedioxy-i 2,2′-biphenyldiyldi-oxy-) to yield the mixed donor group tripodal ligands X2POCH(CH2PR2)(CH2PR2) (5, 8) containing both phosphite, phosphinite or phosphorodichloridite and phosphane donor groups. The identity of these compounds were proved by 'H-, 31P- and 13C-NMR spectroscopy, mass spectra, microanalysis as well as X-ray analysis. The coordination capabilities of these novel ligands are demonstrated by the synthesis and characterization of a (cyclooctadiene)rhodium complex {[(5c)Rh(I)COD]PF6) (7) of the ligand 5c, exhibiting the typical hetero-bicyclooctane tripod metal cage of this type of tripod complexes. VCH Verlagsgesellschaft mbH, 1996.
