A comparison of the reactivity of germylene and dimethylgermylene with some methylgermanes. Direct kinetic and quantum chemical studies.
Time-resolved studies of germylene, GeH(2), and dimethygermylene, GeMe(2), generated by the 193 nm laser flash photolysis of appropriate precursor molecules have been carried out to try to obtain rate coefficients for their bimolecular reactions with dimethylgermane, Me(2)GeH(2), in the gas-phase. GeH(2) + Me(2)GeH(2) was studied over the pressure range 1-100 Torr with SF(6) as bath gas and at five temperatures in the range 296-553 K. Only slight pressure dependences were found (at 386, 447 and 553 K). RRKM modelling was carried out to fit these pressure dependences. The high pressure rate coefficients gave the Arrhenius parameters: log(A/cm(3) molecule(-1) s(-1)) = -10.99 +/- 0.07 and E(a) =-(7.35 +/- 0.48) kJ mol(-1). No reaction could be found between GeMe(2) + Me(2)GeH(2) at any temperature up to 549 K, and upper limits of ca. 10(-14) cm(3) molecule(-1) s(-1) were set for the rate coefficients. A rate coefficient of (1.33 +/- 0.04) x 10(-10) cm(3) molecule(-1) s(-1) was also obtained for GeH(2) + MeGeH(3) at 296 K. No reaction was found between GeMe(2) and MeGeH(3). Rate coefficient comparisons showed, inter alia, that in the substrate germane Me-for-H substitution increased the magnitudes of rate coefficients significantly, while in the germylene Me-for-H substitution decreased the magnitudes of rate coefficients by at least four orders of magnitude. Quantum chemical calculations (G2(MP2,SVP)//B3LYP level) supported these findings and showed that the lack of reactivity of GeMe(2) is caused by a positive energy barrier for rearrangement of the initially formed complexes. Full details of the structures of intermediate complexes and the discussion of their stabilities are given in the paper.
Instituto de Quimica-Fisica Rocasolano, Consejo Superior de Investigaciones Científicas, C/Serrano 119, 28006 Madrid, Spain.
Rosa
R
Becerra
Sergey E
SE
Boganov
Mikhail P
MP
Egorov
Valery I
VI
Faustov
Irina V
IV
Krylova
Oleg M
OM
Nefedov
Vladimir M
VM
Promyslov
Robin
R
Walsh
D002627:Chemistry, Physical / Q000379:methods*; D005609:Free Radicals / Q000737:chemistry*; D005740:Gases; D005857:Germanium / Q000737:chemistry*; D007700:Kinetics; D008956:Models, Chemical; D008962:Models, Theoretical; D008968:Molecular Conformation; D015394:Molecular Structure; D011312:Pressure; D011789:Quantum Theory; D013696:Temperature
D005609:Free Radicals; D005740:Gases; D005857:Germanium