Facile syntheses of the meso-tetra-p-tolylporphyrin (TTP) complexes trans-(TTP)Ti(THF)2(1), (TTP)Sn (2), and trans-(TTP)V(THF)2 (3) are achieved through homogeneous reduction of high-valent precursors using NaBEt3H. The composition of the new compound trans-(TTP)Ti(THF)2 was determined by spectroscopic and chemical characterization. Ligand displacement reactions of trans-(TTP)Ti(THF)2 with t-BuNC produced a new Ti(II) complex,trans-(TTP)Ti(t-BuNC)2. The ligand-binding preference of (TTP)TiIILn (n = 1, 2) is picoline ∼pyridine > t-BuNC > PhC⋮CPh > EtC⋮CEt > THF.
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