Trapping of a Ruthenium−Butatrienylidene Intermediate by Tertiary Amines. 2-Ammoniobutenynyl Complexes | Zendy

Rainer F. Winter | Zendy; Fridmann M. Hornung | Zendy

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Trapping of a Ruthenium−Butatrienylidene Intermediate by Tertiary Amines. 2-Ammoniobutenynyl Complexes

Author(s) -

Rainer F. Winter,

Fridmann M. Hornung

Publication year - 1999

Publication title -

organometallics

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.231

H-Index - 172

eISSN - 1520-6041

pISSN - 0276-7333

DOI - 10.1021/om9903240

Subject(s) - chemistry , amine gas treating , pyridine , ruthenium , delocalized electron , medicinal chemistry , ligand (biochemistry) , substituent , cyclic voltammetry , electron paramagnetic resonance , yield (engineering) , electrochemistry , redox , derivative (finance) , stereochemistry , catalysis , inorganic chemistry , organic chemistry , biochemistry , physics , receptor , materials science , electrode , nuclear magnetic resonance , economics , financial economics , metallurgy

2-Ammoniobutenynyl Ru-complexes trans-[Cl(dppm)2Ru−C⋮C−C(NR2R‘)CH2]+PF6- (3a−g) have been prepared in a one-pot procedure from cis-[RuCl2(dppm)2], excess butadiyne, and various tertairy amines, whereas 4-(dimethylamino)pyridine binds to the unsaturated carbon ligand via the pyridine nitrogen to give 3h. These results may be rationalized by envoking the butatrienylidene complex trans-[Cl(dppm)2RuCCCCH2]+ as the reactive intermediate. Amine complexes cis-[Ru(dppm)2Cl(NR2R‘)]+ are frequently formed as side products and the 4-dimethylaminopyridine derivative cis-[Ru(dppm)2Cl(4-DMAP)]+ was obtained in high yield in the absence of butadiyne but under otherwise identical reaction conditions. Complexes 3 have been characterized by various spectroscopic and electrochemical techniques including cyclic and square wave voltammetry and, in the case of the NEt3 derivative 3a, also by X-ray crystallography. Most complexes 3 undergo a fully reversible one-electron oxidation at half-wave potentials that depend on the amin...

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