Amido-derivatives of metals and metalloids. Part XIV. Reactions of titanium(III) dimethylamides with protic or unsaturated reagents, or with metal hydrides

Abstract

Titanium(III) dimethylamides {[(π-C₅H₅)_3–nTi(NMe₂)_n]₂n= 1, 2, 3} are versatile synthetic reagents. They react with (i) protic reagents (ROH: R = Me, Et, Ph; o-C₆H₄(OH)₂; PhSH) to yield the corresponding alkoxy-, aryloxy-, or phenylthio-derivatives, or (n= 3) with PhOH the complex Ti(OPh)₄,Me₂NH; (ii) unsaturated reagents (PhCN, PhNCO, PhNCS, CS₂) to yield insertion products; (III) Me₃SnH or (π-C₅H₅)Mo(CO)₃H to yield titanium-(III)-metal-bonded complexes; or (iv) the chlorohydride complexes trans-(R₃P)₂Pt(H)Cl (R₃P = Me₂PPh or Ph₃P) which are dehydrochlorinated, possibly via a Ti–Pt-bonded intermediate.

The complexes [(π-C₅H₅)₂TiOEt]₂ and (π-C₅H₅)₂TiMo(CO)₃(π-C₅H₅),0·5THF were also prepared by alternative syntheses.

The complexes [(π-C₅H₅)₂TiOR]₂(R = Et, Ph) and [(π-C₅H₅)₂TiMo(CO)₃(π-C₅H₅) are paramagnetic, while the complexes [Ti(OR)₃]_n(R = Me, Et; R₂=o-C₆H₄), [(π-C₅H₅)₂TiSPh]₂, and the insertion products are diamagnetic.