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The Reactivity of Mercapto Groups against Boron Hydrides in Pincer Ligated Nickel Mercapto Complexes.

Several pincer ligated nickel mercapto complexes, [2,6-(R2 PCH2 )2 C6 H3 ]NiSH (R=tBu, 1 a; iPr, 1 b), [2,6-(R2 PO)2 C6 H3 ]NiSH (R=tBu, 2 a; iPr, 2 b) and [4-MeOCO-2,6-(tBu2 PO)2 C6 H2 ]NiSH (3 a), were synthesized and fully characterized. The reactivity of the mercapto groups against boron hydrides and organic bases was investigated. It was found that the mercapto groups are difficult to be deprotonated by boron hydrides or organic bases. The treatment of complex 2 a or 2 b with an excess amount of catecholborane (HBcat) afforded the corresponding pincer ligated nickel borohydride complexes and the HBcat degradation product. The treatment of complex 1 a, 2 a or 2 b with an excess amount of BH3 ⋅THF produced the corresponding nickel borohydride species and the S-bridged triborane species THF⋅BH2 -μ2 -S(B2 H5 ) (5). No reactions between these complexes and organic bases were observed. DFT calculations were carried out to understand this reactivity and get mechanistic insights into the reactions.