The titanyl complex, TiO(C 22 H 12 N 4 ), a complex of the ligand (I) obtained by the hydrolysis of the corresponding dichloride, has a reactive Ti=O function which readily interacts with other metal species forming~·oxo heterobinuclear dimers. In these adducts, the Ti=O functions as a base toward oxophilic metal centres such as Fe(III) and as a It-acid, analogous to the carbonyl group, forming an adduct with a low valent species such as the Mo (CO), group, yielding a Ti(IV)-O-Mo linkage. Crystals of the titanyl complex, TiO(C22HuN4),C202H6' are monoclinic, nl/C with a = 23.083(3), b = 7.740(7), c = 23.208(5) A,~=96.54. (2) and d(calcd) = 1.443 g cm -3 for Z =4. The Ti=O distance is 1.653(3) Awith a large displacement of 0.754(3) A for the Ti atom from the N 4 macrocyclic coordination plane. The adduct of the titanyl complex with Fe(SALEN)CI, SALEN = (salicylaldimine)ethylenediamine, in the presence of NaB(C 6 H')4 yields a~-oxo-heterobinuclear complex_of stoichiometry (C n H 12 N 4 )Ti-Q-Fe-(SALEN)B(C 6 H')4' Crystals of the complex are triclinic, PI with a = 13.122(4), b = 13.883(12), c = 14.539(5) A, a =94.21(5),~= 93.08(3), ' Y = 99.46(3)" with d(calcd) = 1.336 g cm-3 for Z =2. In addition to the expected dimeric Ti-Q-Fe structure, weak interactions between the SALEN oxygen atoms and the iron atom of the centrosymmetrically related Fe(SALEN) group yields a tetrameric cluster,Ti-Q-Fe~)e-o-Ti. The Ti-Q distance of the Ti-Q-Fe linkage is lengthened to 1.706(4) A and the Fe-Q distance is 1.935(6) Awith the Ti-Q-Fe angle 160.9(2)°. The Fe-Q "intramolecular" interaction distance, 2.178 A, is indicative of a weak bond.
