High yields of the ethoxo-alpha-aminoacidates of the general formula M(OEt)(4)[OC(O)CHRNHR'-kappa O,kappa N] (M = Nb, R = CH2Ph, R' = H, 2; R = CHMe2, R' = H, 3; R = CH2CHMe2, R' = H, 4; R = H, R' = Me, 5; R = CH2CH2SMe, R' = H, 6; M = Ta, R = CH2Ph, R' = H, 7; R = CH2CH2SMe, R' = H, 8) and M(OEt)(4)(OC(O)CH(CH2CH2CH2)NH-kappa O,kappa N) (M = Nb, 9; Ta, 10) have been obtained by the reaction of the L-enantiopure alpha-amino acid (or sarcosine) with a slight molar excess of M(OEt)(5) (M = Nb, 1a; Ta, 1b) in a dichloromethane solution. The new complexes 2-10 have been fully characterized by spectroscopic and analytical methods and by X-ray diffraction for 2 and 7-9. Such X-ray structures are the first ones ever reported for niobium and tantalum coordination compounds containing an alpha-aminoacidato ligand. The early-late heterobimetallic derivative Ta(OEt)(4)[O2CCH(NH2)CH2CH2S(CH3)(AuCl)] (11) has been prepared by the reaction of 8 with a stoichiometric amount of Au(CO)Cl. The bulk polymerization of D,L-lactide initiated by complexes 2 and 7 gave a slightly heterotactic enchainment (P-r = 0.54 and 0.63, respectively), whereas complexes 1a and 1b formed fully atactic polylactide with P-r approximate to 0.4.

Synthesis, X-Ray Characterization and Reactivity of m-Aminoacidato Ethoxide Complexes of Niobium(V) and Tantalum(V)

MARCHETTI, FABIO;PAMPALONI, GUIDO;
2013

Abstract

High yields of the ethoxo-alpha-aminoacidates of the general formula M(OEt)(4)[OC(O)CHRNHR'-kappa O,kappa N] (M = Nb, R = CH2Ph, R' = H, 2; R = CHMe2, R' = H, 3; R = CH2CHMe2, R' = H, 4; R = H, R' = Me, 5; R = CH2CH2SMe, R' = H, 6; M = Ta, R = CH2Ph, R' = H, 7; R = CH2CH2SMe, R' = H, 8) and M(OEt)(4)(OC(O)CH(CH2CH2CH2)NH-kappa O,kappa N) (M = Nb, 9; Ta, 10) have been obtained by the reaction of the L-enantiopure alpha-amino acid (or sarcosine) with a slight molar excess of M(OEt)(5) (M = Nb, 1a; Ta, 1b) in a dichloromethane solution. The new complexes 2-10 have been fully characterized by spectroscopic and analytical methods and by X-ray diffraction for 2 and 7-9. Such X-ray structures are the first ones ever reported for niobium and tantalum coordination compounds containing an alpha-aminoacidato ligand. The early-late heterobimetallic derivative Ta(OEt)(4)[O2CCH(NH2)CH2CH2S(CH3)(AuCl)] (11) has been prepared by the reaction of 8 with a stoichiometric amount of Au(CO)Cl. The bulk polymerization of D,L-lactide initiated by complexes 2 and 7 gave a slightly heterotactic enchainment (P-r = 0.54 and 0.63, respectively), whereas complexes 1a and 1b formed fully atactic polylactide with P-r approximate to 0.4.
Hayatifar, M; Marchetti, Fabio; Pampaloni, Guido; Zacchini, S.
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/11568/208847
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