Synthesis and Reactivity of Ruthenium Vinylidene and Allenylidene Complexes

• Main Authors: Hui-Ling Sung, 宋蕙伶
• Other Authors: Ying-Chih Lin
• Format: Others
• Language: en_US
• Published: 2005
• Online Access: http://ndltd.ncl.edu.tw/handle/64470822251899155692

博士 === 國立臺灣大學 === 化學研究所 === 93 === Ruthenium cyclopropenyl complexes can be obtained by the deprotonation reaction of the ruthenium vinylidene complexes. When the vinylidene complexes containing an ester group at Cγ the reaction yielded thermodynamic ruthenium furyl complexes products. The reaction of the ruthenium cyclopropenyl complexes 6 containing a cyclohexenyl group at Cβ with TMSN3 (TMS = (CH3)3Si) yielded the ruthenium azide [Ru]-N3 ([Ru] = Cp(PPh3)2Ru) and free organic compound 7. The reaction may proceed by an electrophilic addition of a trimethylsilyl group to the three-membered-ring followed by hydrolysis to afford [[Ru]=C=C(C6H9)CH2R][N3]. Further nucleophilic addition of azide at Cα and electrophilic addition of a second trimethylsilyl group at the olefinic carbon of cyclohexenyl ring followed by loss of N2 gave the N-coordinated nitrile complexes [[Ru]NCC(C6H10)CH2R][N3] (9). Change the triphenylphosphine ligand for dppe ligand, the ruthenium furyl complex 12a and cyclopropenyl complex 12d containing cyclohexenyl group also can be obtained via deprotonation of vinylidene complexes 11. Further reaction of the metal furyl complex 12a with O2 yielded diester complex 13a. The reaction of cyclopropenyl complex 12d with TMSN3 gave the N-coordinated nitrile complex 14d as stable product. Change the cyclopentadienyl ligand for indenyl ligand, ruthenium vinylidenecomplexes 16 also can be obtained in high yield. Deprotonation of these vinylidene complexes yielded metal furyl complexes 18 when an ester substituent at Cγ and yielded cyclopropenyl complexes 17. The reaction of the ruthenium α-alkoxyfuryl complexes 18 containing indenyl group with TMSN3 gives the ruthenium azide [Ru]-N3 ([Ru]=(η5-C9H7)(PPh3)2Ru) and organic compounds 5. Treatment of the cyclopropenyl complexes 17 with TMSN3 also affords the ruthenium azide and organic compounds via opening the three-membered ring. Ruthenium isocyanide complex 21 containing indenyl ligand can be obtained in high yield. By deprotonation of these isocyanide complex yield ruthenium azirine 22 in CH2Cl2 and yield oxazoline complexes 23 in acetone, respectively. The cationic ruthenium allenylidene complex 24 containing a dppe ligand can be synthesized by the literature method. Then the allenylidene complex reacts with Grignard reagents to yield the σ−alkynyl derivatives 25a−25d. Protonation of 25a with HBF4·Et2O leads to the vinylidene complex 27a as the final product. Similarly, the vinylidene complex 26 also can be obtained. Protonation of complex 25b yielded the unexpected product 28b. The trans-chloride-ruthenium-allenylidene complexes react with Grignard reagents to yield the σ−alkynyl derivatives 29. Protonation of 29 with HBF4·Et2O also leads to the vinylidene complex 30. Complex 30 is stable in solid state. When dissolved inCH2Cl2 at room temperature the organic enyne product 31 can be obtained through the demetalation reaction. The trans-isocyanide-ruthenium-alkyne complexes 33 also can be obtained in high yield. The trans-chloride-ruthenium-alkyne 34 and dialkynyl complex 36 containing cyclohexenyl group also can be obtained in moderate yield. Both complexes are stable.