NSO-Donor Ligands

NO- and NSO-Donor Ligands. Co-ordination of Ti with o-phen (L) is stepwise with the formation of [TiL(H2 0)4] , [TiL2(H20)2], and [TiLj]. According to i.r. evidence, o-hydroxy-4-benzamidothiosemicarbazide (L) binds to Ti through the phenolic O, thioketone S, and amide N atoms in the complex [TiL2]Cl7  

A method for the preparation of the thioether complexes (Cp2Ti SR)2 (R = Me, Ph, PhCH2 or p-tolyl) has been patented (see also Vol. 5, p. 7). 

The dinitrogen complex (Cp2TiR)2N2 liberates Nj and RH (R = Ph, m- or p-MeCgH4, or CH2Ph) on thermal decomposition, the decomposition residue evolves 

Kinetic data have been obtained on the hexa-aquotitanium(iii) reduction of a series of Co complexes from comparison of rate constants with those for [Ru(NH3) ] and reduction of the same complexes it was concluded that the Ti reduction of the p-superoxo-complex [(NH3)5Co02Co(NH3)5] , Co(NH3)5804, and Co-(NH3)5(OAc)2 are inner-sphere with [Co(NH3)5X] (X = Cr, Br , 1 , NH3, or H2O) and [Co(bipy)3] reduction is outer-sphere. It is noteworthy that the inner-sphere reduction occurs with hard-base ligand complexes since Ti ion is to be regarded as a hard-acid ion. With salicylatocobalt(iii) as reducible sub- 

TiCl4 and LiBH4 afford Ti(BH4)3, whereas with LiAlH4 at 163 K in ether Ti(AlH4)4 is obtained (see p. 22). 

---