Unusual room temperature activation of 1,2-dialkoxyalkanes by niobium and tantalum pentachlorides.
The outcome of the reactions of MCl(5) (M = Nb, 1a; M = Ta, 1b) with 1,2-dialkoxyalkanes [i.e. MeO(CH(2))(2)OMe (dme), EtO(CH(2))(2)OEt, MeOCH(2)CH(Me)OMe, MeO(CH(2))(2)OCH(2)Cl, MeO(CH(2))(2)O(CH(2))(2)OMe (diglyme)] depends strictly on the stoichiometry. In the 1 : 1 molar ratio reactions, single C-O bond cleavage occurs, resulting in formation of alkyl chloride and of the complexes [upper bond 1 start]MCl(4)[O(R)CH(R')CH(2)O][upper bond 1 end] [M = Nb, R = Me, R' = H, 3a; M = Ta, R = Me, R' = H, 3b; M = Nb, R = Et, R' = H, 5; M = Nb, R = R' = Me, 6; M = Nb, R = CH(2)Cl, R' = H, 7; M = Nb, R = (CH(2))(2)O(Me)NbCl(5), R' = H, 8], which have been characterized spectroscopically. Moreover, minor amounts of the oxo-bridged adducts MOCl(3)(dme)MCl(5) (M = Nb, 4a; M = Ta, 4b) have been isolated in the reactions involving dme. On the other hand, compounds react with two (or more) equivalents of dme mainly via a multiple C-O bond cleavage process, affording MOCl(3)(dme) (M = Nb, 2a; M = Ta, 2b), 1,4-dioxane and methyl chloride. The oxychloride compounds MOCl(3) (M = Nb, 11a; M = Ta, 11b) have been efficiently obtained by addition of TiCl(4) to 2. Compound 2a is reduced in high yield to the Nb(III) species NbCl(3)(dme), 12, upon treatment with SnBu(3)H. The oxychloride NbOCl(3)(diglyme), 9, 1,4-dioxane, CH(3)Cl and the hexachloroniobate salt [MeOCH(2)CH(2)OCH(2)CH(2)O(H)Me][NbCl(6)], 10, have been identified as products of the reaction of 1a with two equivalents of diglyme. The 1 : 2 molar ratio reaction of 1a with MeOCH(2)CH(Me)OMe gives 2,5-dimethyl-1,4-dioxane. Compound 1a reacts with two equivalents of EtO(CH(2))(2)OEt or MeO(CH(2))(2)OCH(2)Cl yielding Cl(CH(2))(2)OCH(2)CH(3) or O(CH(2)Cl)(2) and diglyme, respectively, but not dioxane, suggesting that fragmentation pathways different from that found for dme are operating. The X-ray molecular structures of 4a, 4b and 10 have been determined.
Marchetti
Fabio
F
Università di Pisa, Dipartimento di Chimica e Chimica Industriale, Pisa, Italy.
Pampaloni
Guido
G
Zacchini
Stefano
S
D000438:Alcohols / Q000737:chemistry*; D000473:Alkanes / Q000737:chemistry*; D002712:Chlorides / Q000138:chemical synthesis / Q000737:chemistry*; D009556:Niobium / Q000737:chemistry*; D010084:Oxidation-Reduction; D013635:Tantalum / Q000737:chemistry*; D013696:Temperature
D000438:Alcohols; D000473:Alkanes; D002712:Chlorides; C059688:alkoxyl radical; D009556:Niobium; D013635:Tantalum; C535111:niobium pentachloride; C535112:tantalum pentachloride