182002-47-7Relevant academic research and scientific papers
Zirconium alkyl thiolate complexes:Synthesis and reactivity.Molecular structures of[Zr(η5-C5H5)2(η 2-C6H7N2S)(Me)]and[Zr(η5- C5H5)2(η1-C6H7N 2S)
Fandos, Rosa,Lanfranchi, Maurizio,Otero, Antonio,Pellinghelli, Maria Angela,Ruiz, María José,Terreros, Pilar
, p. 4725 - 4730 (1996)
The thiolate-alkylzirconocene complex Cp2ZrMe(SR) (2) (Cp = η5-C5H5; SR = 4,6-dimethylpyrimidine-2-thiolate) can be prepared by reacting the corresponding dialkylmetallocene complex Cp2ZrMe2 (1) with 1 equiv of 4,6-dimethyl-2-mercaptopyrimidine. X-ray structure analysis of complex 2 revealed that the thiolate group is bonded in an η2 fashion through the sulfur and one of the nitrogen atoms. Complex 2 reacts with 2,6-dimethylphenyl isocyanide (CNXylyl) to yield the corresponding iminoacyl derivative, Cp2Zr(η2-MeCNXylyl)-(SR) (4). The molecular structure of 4 shows that the thiolate group is η1-bonded while the iminoacyl group behaves as a bidentate ligand. Reaction of compound 2 with different acidic reagents gives formation of methane and different zirconium complexes. Reaction with HSR renders Cp2Zr(SR)2 (3) and with (NHEt3)(BPh4) the cationic complex [Cp2Zr(SR)][BPh4] (5). An hydride thiolate complex, Cp*2ZrH(SR) (Cp* = η5-C5Me5) (6) can also be prepared by reaction of Cp*2Zr with HSR by an oxidative addition reaction.
