| Abstract
| - Themethyl−thiolate zirconocene complex Cp2ZrMe(SR)was prepared by reacting the corresponding dialkylmetallocene complexCp2ZrMe2 with4,6-dimethyl-2-mercaptopyrimidine.Cp2ZrMe(SR) reacts with 2,6-dimethylphenylisocyanide (CNXylyl) to yield the corresponding iminoacyl complex,Cp2Zr(η2-MeCNXylyl)(SR).Reaction of Cp2ZrMe(SR) with HSR rendersCp2Zr(SR)2 and with(NHEt3)(BPh4) yields the cationic complex[Cp2Zr(SR)][BPh4]. Anhydride thiolate complex, Cp*2ZrH(SR) (Cp* =η5-C5Me5) can also beprepared by reaction of “Cp*2Zr” with HSR by anoxidative addition reaction.
- The thiolate−alkylzirconocene complexCp2ZrMe(SR) (2) (Cp =η5-C5H5; SR = 4,6-dimethylpyrimidine-2-thiolate) can be prepared by reacting thecorresponding dialkylmetallocene complex Cp2ZrMe2 (1)with 1 equiv of 4,6-dimethyl-2-mercaptopyrimidine.X-raystructure analysis of complex 2 revealed that the thiolategroup is bonded in an η2 fashionthrough the sulfur and one of the nitrogen atoms. Complex2 reacts with 2,6-dimethylphenylisocyanide (CNXylyl) to yield the corresponding iminoacyl derivative,Cp2Zr(η2-MeCNXylyl)(SR) (4). The molecular structure of 4 showsthat the thiolate group is η1-bonded whiletheiminoacyl group behaves as a bidentate ligand. Reaction ofcompound 2 with different acidicreagents gives formation of methane and different zirconium complexes.Reaction with HSRrenders Cp2Zr(SR)2 (3) andwith (NHEt3)(BPh4) the cationic complex[Cp2Zr(SR)][BPh4](5).An hydride thiolate complex, Cp*2ZrH(SR)(Cp* = η5-C5Me5)(6) can also be prepared byreaction of “Cp*2Zr” with HSR by an oxidativeaddition reaction.
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