ISSN:
1434-1948
Keywords:
C-C coupling
;
Metallacycles
;
Metallacyclobutane
;
Ruthenium
;
Tripodal ligands
;
Vinylidene complexes
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Selective coupling of olefins and terminal acetylenes is shown to be effected in the coordination sphere of RuII by the successive intermediacy of vinylidene and ruthenacyclobutane complexes. Subsequent deprotonation of one of the β-hydrogen atoms of the latter by NaOEt yields η3-butadienyl complexes, while in the presence of Cl- rearrangement takes place to give neutral η2-butadiene complexes by a β-hydrogen elimination/reductive elimination sequence. [Ru(tp)(COD)Cl] and [Ru(tp){η3-(P,C,C)-Ph2PCH=CHC(Ph)=CH2}Cl] were the starting materials which were treated with HC≡CR (R = Ph, C6H9, ferrocenyl, CH2Ph, nBu). The η3-butadienyl complexes are nucleophilic at the enynyl carbon atom reacting readily with the electrophiles H+ and I2 to give the corresponding η2-butadienyl complexes. X-ray structures of representative products are given.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
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