0000000000217678
AUTHOR
Pascual Royo
Chelated η5-cyclopentadienyl-η-ethyl complexes of molybdenum and tungsten; molecular structure of W(η5-C5H4CH2-η-CH2)(CO)3
Abstract Molybdenum and tungsten complexes M(η5-C5H4CH2-η-CH2)(CO)3 (M=Mo, W) containing the bidentate ethyl-functionalized cyclopentadienyl ligand C5H4CH2CH2 have been synthesized by the reaction of spiro[2.4]hepta-4,6-diene with M(CO)3L3 (M=Mo; L3=1,3,5-C6H3Me3; M=W; L=NCMe). Reaction of the more stable tungsten complex with C6H5ICl2 and HBF4 gave complexes of the type W(η5-C5H4CH2CH2Cl)(CO)3Cl, W(η5-C5H4CH2CH3)(CO)3Cl and W(η5-C5H4CH2CH3)(CO)3(FBF3), respectively. The crystal structure of the tungsten tricarbonyl complex W(η5-C5H4CH2-η-CH2)(CO)3 has been determined by X-ray crystal diffraction on a single crystal and shows a four-legged piano stool structure.
Diastereoselective Insertion of Isocyanide into the Alkyl−Metal Bond of Methylbenz[ e ]indenyl ansa ‐Zirconocene Complexes
Alkylation of ansa-zirconocene [Zr{(η5-C5H5)SiMe2(MBI)}Cl2] (MBI = η5-2-Me−C13H7) with MgRCl gave the dimethyl complex [Zr{(η5-C5H5)SiMe2(MBI)}Me2], but unresolvable mixtures containing mono-alkylated compounds were obtained when bulkier alkyls were used. However pure dialkyl complexes [Zr{(η5-C5H5)SiMe2(MBI)}R2] (R = CH2Ph, CH2SiMe3) were easily obtained using K(CH2Ph) and Li(CH2SiMe3) as alkylating agents. Diastereoselective insertion into the MBI-unprotected Zr−R bond was observed when all of these dialkyl complexes were treated with 2,6-xylyl isocyanide to give the iminoacyl compounds [Zr{(η5-C5H5)SiMe2(MBI)}R{CR[η2-N-(2,6-xylyl)]}] (R = Me, CH2Ph, CH2SiMe3). All of the new complexes we…
Synthesis and characterization of titanium(IV) complexes containing the diphenylphosphino- and diphenylthiophosphoryl-functionalized cyclopentadienyl ligand. Crystal and molecular structure of Ti(η5-C5H4PPh2)Cl3
The trimethylsilyl cyclopentadiene derivative C5H4(SiMe3)PPh2 (1) was treated with TiCl4 to give the air- and moisture-sensitive mono(cyclopentadienyl) compound Ti(η5-C5H4PPh2)Cl3 (4). Reaction of 4 with Mg(CH2C6H5)2(THF)2 gave Ti(η5-C5H4PPh2)(CH2C6H5)3 (5). Reactions of the lithium and thallium derivatives M{C5H4P(S)Ph2} (M=Li (2), Tl (3)) with one equiv. of TiCl4 afforded the mono(cyclopentadienyl) complex Ti{η5-C5H4P(S)Ph2}Cl3 (6), whereas reaction with 0.5 equiv. of TiCl4 gave the bis(cyclopentadienyl) complex Ti{η5-C5H4P(S)Ph2}2Cl2 (8). Compound 6 was also isolated as a minor product from the reaction of Ti{η5-C5H4P(S)Ph2}2Cl2 (8) with one equiv. of TiCl4. The major product was identif…