Gallium "Shears" for C=N and C=O Bonds of Isocyanates

Digallane [L¹ Ga-GaL¹ ] (1, L¹ =dpp-bian=1,2-[(2,6-iPr₂ C₆ H₃ )NC]₂ C₁₂ H₆ ) reacts with RN=C=O (R=Ph or Tos) by [2+4] cycloaddition of the isocyanate C=N bonds across both of its C=C-N-Ga fragments to afford [L¹ (O=C-NR)Ga-Ga(RN-C=O)L¹ ] (R=Ph, 3; R=Tos, 4). The reactions with both isocyanates result in new C-C and N-Ga single bonds. In the case of allyl isocyanate, the [2+4] cycloaddition across one C=C-N-Ga fragment of 1 is accompanied by insertion of a second allyl isocyanate molecule into the Ga-N bond of the same fragment to afford compound [L¹ Ga-Ga(AllN- C=O)₂ L¹ ] (5) (All=allyl). In the presence of Na metal, the related digallane [L² Ga-GaL² ] (2; L² =dpp-dad=[(2,6-iPr₂ C₆ H₃ )NC(CH₃ )]₂ ) is converted into the gallium(I) carbene analogue [L² Ga:]^- (2 A), which undergoes a variety of reactions with isocyanate substrates. These include the cycloaddition of ethyl isocyanate to 2 A affording [Na₂ (THF)₅ ]{L² Ga[EtN-C(O)]₂ GaL² } (6), cleavage of the N=C bond with release of 1 equiv. of CO to give [Na(THF)₂ ]₂ [L² Ga(p-MeC₆ H₄ )(N-C(O))₂ -N(p-MeC₆ H₄ )]₂ (7), cleavage of the C=O bond to yield the di-O-bridged digallium compound [Na(THF)₃ ]₂ [L² Ga-(μ-O)₂ -GaL² ] (8), and generation of the further addition product [Na₂ (THF)₅ ][L² Ga(CyNCO₂ )]₂ (9). Complexes 3-9 have been characterized by NMR (¹ H, ¹³ C), IR spectroscopy, elemental analysis, and X-ray diffraction analysis. Their electronic structures have been examined by DFT calculations.