Matrix Isolation and Density Functional Study of the Reaction of OVCl₃ with CH₃OH:  Synthesis and Characterization of Cl₂V(O)OCH₃

Abstract

The matrix isolation technique has been employed to investigate the reaction of OVCl3 with CH3OH. Using twin jet deposition, the initial intermediate in the mechanism was identified as a weakly bound molecular complex. This species is characterized by perturbations to the C−O, VO, and V−Cl stretching modes. Merged jet deposition, with a room-temperature reaction zone, led to complete conversion to Cl2V(O)OCH3, the second intermediate in the reaction sequence, through HCl elimination from the initial complex. This species was identified by use of extensive isotopic labeling, the observation of HCl as an additional reaction product, and by comparison to density functional calculations. All of the fundamental vibrational modes of this species that lie above 400 cm-1 were observed, some with very high intensities. Heating the reaction zone above 150 °C led to destruction of this intermediate, and production of both CH2O and CH3Cl.

Matrix isolation and theoretical investigation of the photochemical reaction of CrCl2O2 with benzenes substituted with electron withdrawing groups

“…Past studies in this laboratory have examined the matrixisolated products of the thermal and photochemical reactions of CrCl 2 O 2 , OVCl 3 , and OVF 3 with organic and inorganic substrates [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32]. Specifically, two recent studies in this lab [33,34] examined the reactions of CrCl 2 O 2 with benzene and with methyl-substituted benzenes.…”

Matrix Isolation and Theoretical Study of the Photochemical Reaction of CrCl2O2 with Chloroethenes

“…6,7 This laboratory has studied the reaction of these transition-metal compounds and several related species with small organic and inorganic substrates containing a heteroatom. [8][9][10][11][12][13] These studies have permitted the identification of a sequence of intermediates in each system from which a reaction mechanism was (at least partially) deduced. Wistuba and Limberg have focused on the reaction of CrCl 2 O 2 with alkenes and alkynes 14,15 and have reported several novel intermediates.…”

Infrared Matrix Isolation and Density Functional Theory Study of Intermediates in the Reactions of OVCl3 and CrCl2O2 with H2O

“…This approach has been applied to the study of a wide range of species, including radicals, weakly bound molecular complexes, and molecular ions. Recent studies from this laboratory have focused on the sequence of intermediates formed in the reactions of OVCl 3 and CrCl 2 O 2 with small organic substrates, − as well as with NH 3 . , These studies have demonstrated that these reactions occur through the formation of an initial 1:1 complex, followed by thermal and/or photochemical elimination of HCl. In addition, since impurity levels of water are always present in matrix isolation studies, a knowledge of the spectrum of possible reaction products of OVCl 3 and CrCl 2 O 2 with H 2 O is important.…”