Reactions of Ruthenium Complexes Containing Pentatetraenylidene Ligand. Issue 21 (10th October 2016)

• Record Type: Journal Article
• Authors: Tsai, Shih‐Hung; Lin, Ying‐Chih; Liu, Yi‐Hung
• Is Part Of: Chemistry, an Asian journal. Volume 11:Issue 21(2016)
• Page Start: 3072
• Page End: 3083
• Publication Date: 2016-10-10
• Subjects: acetylides -- allenylidenes -- bond cleavage -- pentatetraenylidenes -- ruthenium; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/asia.201601045
• Languages: English
• ISSNs: 1861-4728

Abstract

Abstract: Two ruthenium acetylide complexes [Ru]−C≡C−C≡C−C(OR)(C3 H5 )2 (2, R=H and 2 a, R=CH3 ; [Ru]=Cp(PPh3 )2 Ru) each with two cyclopropyl rings were synthesized from TMS−C≡C−C≡C−C(OH)(C3 H5 )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 NH4 PF6 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 Ph3 CPF6 presumably afforded pentatetraenylidene complex {[Ru]=C=C=C=C=C(C3 H5 )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(C3 H5 )2 }[PF6 ] (11 ). Treatment of 11 with K2 CO3 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. Abstract : R‐u with diyne : Ruthenium acetylide complex 2 a has been synthesized using a 1, 3‐butadiyne ligand. Further addition of trityl ion Ph3 CPF6 presumably generated ruthenium pentatetraenylidene complex 10 . Various nucleophilic reagents were used in a solution of the cumulene complex, and a number of different substituted allenylidene and acetylide complexes were obtained.