A deprotonation reaction of Cp2Ti(SH)2 with NaH in THF yields {Na2[CpTi(μ-S)(S)]2·4THF}2, generated by unexpected elimination of CpH. This anionic dimer is unique in that it is the first organometallic titanium species containing terminal sulfido ligands. The latter are stabilized by interactions with THF-solvated sodium cations, thus imposing a syn TiS configuration.

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The bimetallic compound [Cp*W(NO)(CH2SiMe3)](μ2-η1:η2-NC{H}SiMe3)[Cp*W(Cl)(O)] (1), is produced in low yield by the heterogeneous reaction between Cp*W(NO)(CH2SiMe3)Cl and KOCMe3 in pentane. However, when this reaction is performed in THF or Et2O, the expected metathesis product, Cp*W(NO)(CH2SiMe3)(OCMe3), is obtained. When Cp*W(NO)(CH2SiMe3)Cl is treated with KOMe in pentane, a different bimetallic compound, [Cp*W(NO)(CH2SiMe3)Cl](μ-N)[Cp*W(Cl)(η2-N{O}{H}CH2SiMe3)] (2), is produced along with the known dioxo alkyl complex Cp*W(O)2(CH2SiMe3). Again, the expected alkyl alkoxide product, Cp*W(NO)(CH2SiMe3)(OMe), is produced when the reaction is effected in THF or Et2O. The roles of KOCMe3 or KOMe during the formation of complexes 1 and 2 are presently unclear. However, when the reactions are performed using the Li or Na alkoxide salts, the expected metathesis products, namely the alkyl alkoxide complexes, are indeed produced. The solid-state molecular structures of bimetallic complexes 1 and 2 have been established by single-crystal X-ray crystallographic analyses.