Zirconium-Sulfur Chemistry. Synthesis and Structural Characterization of the Zr3S3(tBuS)2(BH4)4(THF)2, Zr6S6(tBuS)4(BH4)8(THF)2, Zr3(S)(tBuS)10, and (Mg(THF)6)[Zr2(SPh)7.2(CH2Ph)1.8]2.cntdot.3THF Clusters. Activation and Cleavage of the C-S bond in Zirconium-Coordinated Alkanethiolate Ligands

Preparation of Heterobimetallic Oxide–Hydroxide–Hydrogensulfides [LAl(OH)(μ‐O)MCp2(SH)] (M=Ti, Zr)

“…The TiO (1.820 Å) and TiS (2.482 Å) bond lengths and the O‐Ti‐S angle (97.3°) are similar to those reported for other [Cp 2 TiOS] fragments: TiO 1.845–1.872 Å; TiS 2.314–2.467 Å; O‐Ti‐S 87.7–97.9° 11. Furthermore, in the zirconium derivative the ZrO (1.939 Å) and ZrS (2.573 Å) bond lengths and the O‐Zr‐S angle (98.7 Å) are similar to those reported previously for species that contain the {Cp 2 ZrOS} moiety: ZrS 2.459–2.554 Å; ZrO 1.941–2.199 Å; O‐Zr‐S 92.6–103.3° 6b. 12…”

Reactivity of tetrakisdimethylamido-titanium(iv) and -zirconium(iv) with thiols

“…15,26 The Zr-S bond distances are similar to those observed previously in Zr thiolate complexes. [23][24][25] In solution compound 2 appears to retain its solid state structure as shown by the 1 H NMR of 2 where peaks corresponding to the terminal and bridging SBu t groups were observed in a 1 : 2 ratio. This is similar to [Et 2 NH 2 ][Ti 2 (m-SCH 2 Ph) 3 (SCH 2 Ph) 6 ], whereas [Me 2 NH 2 ][Ti 2 (m-SMe) 3 (SMe) 6 ] showed a complex 1 H NMR pattern at room temperature, dissolving to form [Ti 3 (SMe) 12 ] and other compounds.…”

“…Clusters have been obtained from the reaction of 2-methyl-2-propanethiol and [Zr(BH 4 ) 4 ] resulting in the formation of [Zr 3 S 3 (Bu t S) 2 (BH 4 ) 4 (thf) 2 ] or [Zr 6 S 6 (Bu t S) 4 (BH 4 ) 8 (thf) 2 ]. 23,24 In contrast, reaction of the same thiol with [Zr(CH 2 Ph) 4 ] afforded [Zr 3 (S)(SBu t ) 10 ]. 25 In this paper the reactivity of [M(NMe 2 ) 4 ] (M ¼ Ti, Zr) with thiols is described.…”

Formation of sulfido ciobium complexes through C-S bond activation

“…Due to the stability of the C-S bond in aromatic thiolate ligands the clevage of this bond is not common but it is a very important step in the desulphurization of organic fuels 22 . In the reactions described here they occur very easily.…”