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)(TiLn)-L-II (n = 1, 2) is picoline similar to pyridine > t-BuNC > PhC=CPh > EtC=CEt > THF.