Reactivity of platinum iminoboryl complexes toward covalent element-hydrogen bonds of opposing polarity

Article abstract of DOI:10.1021/om1004868

Reaction of the platinum iminoboryl complex trans-[(Cy₃P) ₂(Br)Pt(B≡NSiMe₃)] (Cy = cyclohexyl) toward covalent element-hydrogen bonds of inverse polarity led to regiospecific formation of the corresponding trans products of 1,2-dipolar addition. Hydrogen bromide reversibly adds to the B≡N triple bond, and despite the close proximity of the bromide to the trimethylsilyl substituent, the hydrobromination adduct trans-[(Cy₃P)₂BrPt{B(Br)N(H)SiMe₃}] did not show any signs of bromosilane elimination. Furthermore, the reaction of trans-[(Cy₃P)₂(Br)Pt(B≡NSiMe₃)] and trans-[(Cy₃P)₂Pt(B≡NSiMe₃)(C≡CPh)] with the hydroboration reagent catecholatoborane was probed, revealing in both cases clean 1:1 reaction of the reagents. Whereas the reaction product of the latter complex is inherently unstable, both the mono-and the dinuclear hydroboration products of trans-[(Cy₃P)₂(Br) Pt(B≡NSiMe₃)] could be isolated and fully characterized including X-ray diffraction analysis.