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WE here describe some salts containing a new class of cation, the dialkylideneammonium cation [R,C:N:CR,] +, which is isoelectronic with and apparently isostructural with allenes R,C:C:CR,.Salts of the cations [Ph2C:N:CPh2]+ and [P-tolyl,-C:N:CPh,]+ were prepared in order to study further the interesting relationship that exists between unsaturated organic compounds and cations formally derived from them by replacing a multiply bonded carbon atom by a positively charged nitrogen, e.g., compare alkynes RCiCR with nitrilium cations [RCiNR]+, or alkenes R,C:CR, with imonium cations [R,C:NR,]+. Such cations apparently have the same shape and essentially the same bond multiplicity as the isoelectronic carbon compound, even though in principle the skeletal bond order could be lowered, and the shape at nitrogen changed, by contributions from carbonium ionic forms such as RC+=NR or R,C+-NR,.5The route used for the preparation of the dialkylideneammonium salts was chosen by analogy with a convenient route to nitrilium salts, which result from the action of Lewis acids on imidoyl chlorides [equation (l)] .3 We accordingly investigated the action of Lewis RCC1:NR + MC1, -w [RCiNR]+[MCl, + (1) acids on ketiminomethyl chlorides R2C:NCC1Ph2, a class

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Titanium(IV) complexes of the type [(acac)2Ti(O-G-O] and [(acac)2Ti(OCH2CH2SH)2] {where G = (CH2)2, CH2CH(CH3), CH2CH(C2H5), CH(CH3)CH(CH3) have been synthesized in high yield by the interaction of the precursor [(acac)2Ti( OR)2] {where R = Pri , Et} with a variety of glycols and thioglycols in 1:1 and 1:2 molar ratios in refluxing benzene under anhydrous condition yield heteroleptic derivatives. On the basis of physico-chemical analyses, a cis-octahedral environment around Ti (IV) is proposed.

Titanium complexes of the type [(OPr i )4-nTi(OC2H4OR)n], [(acac)2Ti(O-G-O] and [(acac)2Ti(OPr i )(OCH2CH2SH)] were synthesized from stoichiometric reactions between titanium tetraisopropoxide [(Ti(OPri)4, TPT] and alkoxyalkanols {HOCH2CH2OR} in 1:1 to 1:4 molar ratios, where R = Et and n-Bu and by the interaction of the precursor [(acac)2Ti(OR)2] with different diols and thiol in 1:1 molar ratio, where G = (CH2)2, (CH2)5 and C(CH3)2CH2CH(CH3), R = isoprop. The reactions have been carried out in refluxing benzene under anhydrous conditions to yield mononuclear derivatives. All these compounds were purified by distillation under reduced pressure. On the basis of elemental analysis, IR and NMR ( 1 H and 13 C) spectral studies tetrahedral as well as a cis octahedral geometry around Ti(IV) is proposed.