Cycloaddition versus Cleavage of the C=S Bond of Isothiocyanates Promoted by Digallane Compounds with Noninnocent α‐Diimine Ligands

Abstract

Whereas the chemistry of single-bond activation by compounds of the main group elements has undergone some development in recent years, the cleavage of multiple bonds remains underexplored. Herein, the reactions of two digallanes bearing α-diimine ligands, namely, [L¹ Ga-GaL¹ ] (1, L¹ =dpp-dad=[(2,6-iPr₂ C₆ H₃ )NC(CH₃ )]₂ ) and [L² Ga-GaL² ] (2, L² =dpp-bian=1,2-[(2,6-iPr₂ C₆ H₃ )NC]₂ C₁₀ H₆ ), with isothiocyanates are reported. Reactions of 1 or 2 with isothiocyanates in 1:2 molar ratio proceeded with [2+4] cycloaddition of the C=S bond across the C₂ N₂ Ga metallacycle with formation of C-C and S-Ga single bonds to afford [L¹ (RN=C-S)Ga-Ga(S-C=NR)L¹ ] (3, R=Me; 4, R=Ph) and [L² (RN=C-S)Ga-Ga(S-C=NR)L² ] (8, R=allyl; 9, R=Ph). In the cases of 8 and 9, this cycloaddition is reversible. The digallanes reacted with 2 equiv of PhNCS in the presence of Na metal or at high temperatures through a unique reductive cleavage of the C=S bond to yield the disulfide-bridged digallium species [Na(THF)₃ ]₂ [L¹ Ga(μ-S)₂ GaL¹ ] (5), [L² Ga(μ-S)₂ GaL² ] (10), and [Na(DME)₃ ][L² Ga(μ-S)₂ GaL² ] (11). Moreover, products 4 and 5 can further react with an excess of isothiocyanate, through cleavage of the C=S bond or cycloaddition, to give the bis- or mono-S-bridged complexes [Na(THF)₂ ]₂ [L¹ (PhN=C-S)Ga(μ-S)₂ Ga(S-C=NPh)L¹ ] (6) and [L¹ (PhN=C-S)Ga(μ-S)Ga(S-C=NPh)L¹ ] (7). All the newly prepared compounds were characterized by elemental analysis, single-crystal X-ray diffraction, IR spectroscopy, NMR (3-9) or ESR spectroscopy (11), and DFT calculations.