A series of titanium-phosphinimide thiolate complexes were prepared employing either thiolate for chloride metathesis or protonolysis of metal-carbon bonds by thiols. In these ways the following species were obtained:Reactions of (t-Bu 3 PN) 2 TiMe 2 with 1 equiv of HSCH 2 Ph gave a cyclometalated species 17, (t-Bu 3 PN) 2 Ti(η 2 -SCHPh). The analogous reaction of 1 equiv of phenylthiol generated the species (t-Bu 3 PN) 2 Ti(Me)(SPh) 18. While 17 and 18 could not be isolated free of 14 and 15, respectively, the analogous reaction of tert-butylthiol afforded (t-Bu 3 PN) 2 Ti(Me)(St-Bu) 19 cleanly. Attempts to effect sulfur insertion into Ti-Me bonds were undertaken via the reaction of (t-Bu 3 PN) 2 TiMe 2 with S 8 but gave instead the species (t-Bu 3 PN) 2 Ti(η 2 -S 5 ) 20. The reactivity of the thiolate derivatives, 3-5 with excess AlMe 3 , was examined. Spectroscopic and crystallographic studies revealed the formation of (CpTi(µ-SR)(µ-NPi-Pr 3 )(C)(AlMe 2 ) 2 -(µ-SR)AlMe (R ) CH 2 Ph 21, Ph 22, t-Bu 23). Analogous reactions of 7 and 8 with AlMe 3 afforded [Cp(i-Pr 3 PN)Ti(SRS)]‚(AlMe 3 ) 3 (R ) (CH 2 ) 3 24, ((CH 2 ) 2 (C 6 H 4 )) 25). The mechanistic implications of the observed multiple C-H bond activation are considered. Crystallographic studies of 4, 6, 7, 14, 16, and 20-23 are reported.
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