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

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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.