Reactions of Ruthenium Complexes Containing Pentatetraenylidene Ligand |
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| Authors: | Shih‐Hung Tsai Prof. Dr. Ying‐Chih Lin Yi‐Hung Liu |
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| Affiliation: | Department of Chemistry, National Taiwan University, Taipei, Taiwan |
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| Abstract: | Two ruthenium acetylide complexes [Ru]?C≡C?C≡C?C(OR)(C3H5)2 ( 2 , R=H and 2 a , R=CH3; [Ru]=Cp(PPh3)2Ru) each with two cyclopropyl rings were synthesized from TMS?C≡C?C≡C?C(OH)(C3H5)2 ( 1 ; TMS=trimethylsilyl). Treatments of 2 and 2 a with allyl halide in the presence of KPF6 afforded the vinylidene complexes 3 and 3 a , respectively. When NH4PF6 was used, instead of KPF6, additional ring‐opening reaction took place on one of the three‐membered ring. Treatment of [Ru]Cl with 1,3‐butadiyne ( 6 ), bearing an epoxide ring, afforded acetylide complex 7 with a furyl ring. Treatment of 2 a with Ph3CPF6 presumably afforded pentatetraenylidene complex {[Ru]=C=C=C=C=C(C3H5)2}[PF6] ( 10 ), which was not isolated. Additions of various alcohols in a solution of 10 generated a number of disubstituted allenylidene complexes {[Ru]=C=C=C(OR)?C=C(C3H5)2}[PF6] ( 11 ). Treatment of 11 with K2CO3 afforded the acetylide complex 12 bearing a carbonyl group, characterized by single X‐ray diffraction analysis. Addition of a primary amine to 10 caused cleavage of the farthermost C=C bond and several allenylidene complexes {[Ru]=C=C=C(Me)(NHR)}[PF6] ( 18 ) were isolated. |
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| Keywords: | acetylides allenylidenes bond cleavage pentatetraenylidenes ruthenium |
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