Premium
Reactions of Ruthenium Complexes Containing Pentatetraenylidene Ligand
Author(s) -
Tsai ShihHung,
Lin YingChih,
Liu YiHung
Publication year - 2016
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201601045
Subject(s) - acetylide , ruthenium , chemistry , ring (chemistry) , medicinal chemistry , ligand (biochemistry) , amine gas treating , trimethylsilyl , epoxide , stereochemistry , bond cleavage , catalysis , organic chemistry , biochemistry , receptor
Two ruthenium acetylide complexes [Ru]−C≡C−C≡C−C(OR)(C 3 H 5 ) 2 ( 2 , R=H and 2 a , R=CH 3 ; [Ru]=Cp(PPh 3 ) 2 Ru) each with two cyclopropyl rings were synthesized from TMS−C≡C−C≡C−C(OH)(C 3 H 5 ) 2 ( 1 ; TMS=trimethylsilyl). Treatments of 2 and 2 a with allyl halide in the presence of KPF 6 afforded the vinylidene complexes 3 and 3 a , respectively. When NH 4 PF 6 was used, instead of KPF 6 , 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 Ph 3 CPF 6 presumably afforded pentatetraenylidene complex {[Ru]=C=C=C=C=C(C 3 H 5 ) 2 }[PF 6 ] ( 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(C 3 H 5 ) 2 }[PF 6 ] ( 11 ). Treatment of 11 with K 2 CO 3 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)}[PF 6 ] ( 18 ) were isolated.