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Reaction Pathways for Addition of H2 to Amido-Ditetrylynes R2N–EE–NR2 (E = Si, Ge, Sn). A Theoretical Study
journal contribution
posted on 2013-11-25, 00:00 authored by Markus Hermann, Catharina Goedecke, Cameron Jones, Gernot FrenkingQuantum
chemical calculations of the reaction profiles for addition
of one and two H2 molecules to amido-substituted ditetrylynes
have been carried using density functional theory at the BP86/def2-TZVPP//BP86/def2-TZVPP
level of theory for the model systems L′EEL′ and BP86/def2-TZVPP//BP86/def-SVP
for the real compounds. The hydrogenation of the digermyne LGeGeL
(L = N(SiMe3)Ar*; Ar* = C6H2Me{C(H)Ph2}2-4,2,6) follows a stepwise reaction course. The
addition of the first H2 gives the singly bridged species
LGe(μ-H)GeHL, which rearranges with very low activation barriers
to the symmetrically hydrogenated compound LHGeGeHL and to the most
stable isomer LGeGe(H)2L, which is experimentally observed.
The addition of the second H2 proceeds with a higher activation
energy under rupture of the Ge–Ge bond, yielding LGeH and LGeH3 as reaction products. Energy calculations which consider
dispersion interactions using Grimme’s D3 term suggest that
the latter reaction is thermodynamically unfavorable. The second hydrogenation
reaction LGeGe(H)2L → L(H)2GeGe(H)2L possesses an even higher activation barrier than the bond-breaking
hydrogenation step. Further calculations which consider solvent effects
change the theoretically predicted reaction profile very little. The
calculations of the model system L′GeGeL′ (L′
= NMe2) give a very similar reaction profile. Calculations
of the model disilyne and distannyne homologues L′SiSiL′
and L′SnSnL′ suggest that the reactivity of the amido-substituted
ditetrylynes always has the order Si > Ge > Sn. The most stable
product
of the addition of one H2 to the distannyne L′SnSnL′
is the doubly bridged species L′Sn(μ-H)2SnL′,
which has been experimentally observed when bulky groups are employed.
Analysis of the H2–L′EEL′ interactions
in the transition state for the addition of the first H2 with the EDA-NOCV method reveals that the HOMO–LUMO and LUMO–HOMO
interactions have similar magnitudes.