Page 5 - Interaction of Multiple Bonded and Unsaturated Heavier Main Group Compounds with Hydrogen, Ammonia, Olefins, and Related Molecules

Reactivity of Multiple Bonded and Main Group Compounds Power

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SCHEME 4. Summary of the Reactions of EAr 2 (E = Ge, Sn; Ar = Ar (C 6 H 3 - 2,6-(C 6 H 2 -2,4,6-Me 3 ) 2 )orAr (C 6 H 3 - 2,6-(C 6 H 3 -2,6- Pr 2 ) 2 )) with H 2 and NH 3

FIGURE 4. Calculated energy and drawings of intermediates and transition states with selected distances (Å) and angles (deg) for the reaction of
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SnAr 2 (Ar =C 6 H 3 -2,6(C 6 H 2 -2,4,6Me 3 ) 2 ) with NH 3 at the B3PW91 level.
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the activation resembles that of H 2 with transition metal of the germylene GeAr 2 (Ar =C 6 H 3 -2,6(C 6 H 2 -2,4,6Me 3 ) 2 )
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complexes where interactions with d-orbitals (rather than with H 2 or NH 3 afforded the tetravalent products Ar 2 GeH 2
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s- and p-orbitals) effect activation. and Ar 2 Ge(H)NH 2 exclusively. For the bulkier Ar substituted
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We also investigated the reactivity of other main group GeAr 2 ,treatment with H 2 yielded Ar GeH 3 with Ar Helimina-
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molecules with hydrogen. Divalent germylene, stannylene, tion whereas the reaction with NH 3 yielded Ar 2 Ge(H)NH 2 in
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and plumbylenes were already available in our labora- quantitative yield. In contrast, the reactions ofSnAr 2 and SnAr 2 0
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tory, 36 and their reactions with H 2 or NH 3 afforded consider- with H 2 or NH 3 yielded only divalent products with Ar Hor Ar H
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able variation in behavior as shown in Scheme 4. 37 Treatment elimination. Oddly, no reaction between hydrogen and SnAr 2 #
Vol. 44, No. 8 ’ 2011 ’ 627–637 ’ ACCOUNTS OF CHEMICAL RESEARCH ’ 631