The reactions of M′O(acac)2 [M′ = Ti, V; acac = acetylacetonato anion] with equimolar amounts of MF5 (M = Nb, Ta) in CH2Cl2 afforded Ti(acac)2F2, 1a, and [V(acac)3][MF6] (M = Nb, 4a; M = Ta, 4b), respectively. MOF3 (M = Nb, 2a; M = Ta, 2b) were co-produced from MF5/TiO(acac)2. The intermediate species [TaF4{OTi(acac)2}2][TaF6], 3, was intercepted in the course of the formation of 1a from TiO(acac)2/TaF5. NbCl5 reacted with TiO(acac)2 yielding selectively the previously reported [NbO(acac)Cl2]x, 5, and Ti2(acac)2(μ-Cl)2Cl4, 6. Complex 6 was alternatively obtained from the addition of a two-fold excess of TiCl4 to VO(acac)2. The 1:1 reactions of TiX4 (X = F, Cl) with TiO(acac)2 in dichloromethane gave Ti(acac)2X2 (X = F, 1a; X = Cl, 1b) and TiOX2 (X = F, 7a; X = Cl, 7b). The 1:1 combination of TiX4 (X = F, Cl) with VO(acac)2 led to 1a,b and VOX2 (X = F, 8a; X = Cl, 8b). The μ-oxido compounds (C6F5)3B–O–M′(acac)2 (M′ = Ti, V) underwent fragmentation by [PF6]− in chlorinated solvent, yielding POF3, 9, and [B(C6F5)3F]−, 10, according to NMR studies; 1a and V(acac)3+, respectively, were detected as the metal-containing species. Electrochemical studies were carried out aiming at the full characterization of the products and the observation of possible degradation pathways.
Tiziana Funaioli, Fabio Marchetti, Guido Pampaloni, Stefano Zacchini (2013). Ligand-interchange reactions between M(iv) (M = Ti, V) oxide bis-acetylacetonates and halides of high-valent group 4 and 5 metals. A synthetic and electrochemical study. DALTON TRANSACTIONS, 42, 14168-14177 [10.1039/c3dt51378e].
Ligand-interchange reactions between M(iv) (M = Ti, V) oxide bis-acetylacetonates and halides of high-valent group 4 and 5 metals. A synthetic and electrochemical study
ZACCHINI, STEFANO
2013
Abstract
The reactions of M′O(acac)2 [M′ = Ti, V; acac = acetylacetonato anion] with equimolar amounts of MF5 (M = Nb, Ta) in CH2Cl2 afforded Ti(acac)2F2, 1a, and [V(acac)3][MF6] (M = Nb, 4a; M = Ta, 4b), respectively. MOF3 (M = Nb, 2a; M = Ta, 2b) were co-produced from MF5/TiO(acac)2. The intermediate species [TaF4{OTi(acac)2}2][TaF6], 3, was intercepted in the course of the formation of 1a from TiO(acac)2/TaF5. NbCl5 reacted with TiO(acac)2 yielding selectively the previously reported [NbO(acac)Cl2]x, 5, and Ti2(acac)2(μ-Cl)2Cl4, 6. Complex 6 was alternatively obtained from the addition of a two-fold excess of TiCl4 to VO(acac)2. The 1:1 reactions of TiX4 (X = F, Cl) with TiO(acac)2 in dichloromethane gave Ti(acac)2X2 (X = F, 1a; X = Cl, 1b) and TiOX2 (X = F, 7a; X = Cl, 7b). The 1:1 combination of TiX4 (X = F, Cl) with VO(acac)2 led to 1a,b and VOX2 (X = F, 8a; X = Cl, 8b). The μ-oxido compounds (C6F5)3B–O–M′(acac)2 (M′ = Ti, V) underwent fragmentation by [PF6]− in chlorinated solvent, yielding POF3, 9, and [B(C6F5)3F]−, 10, according to NMR studies; 1a and V(acac)3+, respectively, were detected as the metal-containing species. Electrochemical studies were carried out aiming at the full characterization of the products and the observation of possible degradation pathways.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.