Matrix Isolation Investigation of the Room Temperature and Pyrolytic Reactions of Me2Zn with MeOH and MeSH

Abstract

Matrix isolation and cryogenic thin film approaches have been employed for the synthesis, isolation, and characterization of 1:l and 1:2 complexes of (CH3)2Zn with CH30H and CH3SH. These complexes were characterized by a shifting of certain sensitive vibrational modes of the acid and base subunits in the complex. The ratio of the 1: 1 and 1:2 complexes could be altered by changing the relative amounts of the two reagents employed in a given experiment or by warming the cryogenic thin film from 14 K to as high as 200 K.Merged jet mixtures of (CH3)2Zn with either CH30H and its isotopomers or CH3SH were also pyrolyzed at temperatures as high as 370 "C. For the (CH3)2Zn/CH3OH pair, significant production of C& and CH20 was observed with minor amounts of C2H4. In the (CHs)2Zn/CH3SH experiments a substantial yield of ( C H M and CH4 was obtained. These pyrolytic reactions and products have not been reported previously and may have implications for the chemical vapor deposition of ZnO and ZnS.

Infrared Study of the Surface Species Formed by Sequential Chemical Vapor Deposition of Dimethyl Zinc and Ethanethiol on Hydroxylated Alumina Surfaces

“…It is known from earlier work , that the stretching (ν(Zn−Me)), rocking (ρ(Zn−CH 3 )), and the lower-frequency methyl bending modes (δ(CH 3 )) in the infrared spectra of solid methylzinc complexes are sensitive to coordination of different O-, N-, and S-containing ligands to the Zn center. More recent detailed matrix isolation and cryogenic thin-film spectroscopic studies − of the interaction of DMZ with group V and VI alkyls, hydrides, methanol, and methanethiol have been able to distinguish both 1:1 and 1:2 complexes of DMZ with these ligands. Unfortunately, again due to the high-intensity alumina lattice modes below ∼1000 cm -1 , the methyl rocking, and the ν(Zn−C) stretching modes cannot be observed in our transmission infrared experiment.…”

Matrix-Isolation ESR Studies of the Various Isotopomers of the CH3Zn and ZnH Radicals: Comparisons with ab Initio Theoretical Calculations

“…Hauge and co-workers have reported ZnCH 2 and CH 3 ZnH. Ault and Bai have reported argon-matrix studies of the reaction of (CH 3 ) 2 Zn with group-V and group-VI hydrides, with group-V and group-VI alkyls, and with CH 3 OH and CH 3 SH . Greene and co-workers have reported the reaction of excited metal atoms with methane to generate species of the type CH 3 MH, where M = Zn, Cd, or Hg in argon matrixes; the CH 3 ZnH species produced in this study was found to be photostable and did not yield the CH 3 Zn radical when irradiated with the broad-band output of a 500-W medium-pressure Hg lamp.…”

2 Matrix isolation

“…Co-condensation of Me 2 Zn and MeOH or MeSH with excess argon gives 1+1 and 1+2 complexes. 228 The proportions of these two complexes could be altered by adjusting the ratio of the two reactants, or by annealing the matrix. Pyrolysis experiments have also been carried out, where mixtures of the two reagents are heated to temperatures up to 370 °C prior to deposition.…”