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Updated: Oct 21, 2025
The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Syntheses and Structures of trans-bis(Alkenylacetylide) Ruthenium Complexes
Michael R Hall1, Stephen A Moggach1, Paul J Low1
1School of Molecular Sciences, University of Western Australia, 35 Stirling Highway, Crawley, 6009, Western Australia, Australia.
Abstract:
A series of ruthenium alkenylacetylide complexes trans-[Ru{C≡CC(=CH2 )R}Cl(dppe)2 ] (R=Ph (1 a), c C4 H3 S (1 b), 4-MeS-C6 H4 (1 c), 3,3-dimethyl-2,3-dihydrobenzo[b]thiophene (DMBT) (1 d)) or trans-[Ru{C≡C-c C6 H9 }Cl(dppe)2 ] (1 e) were allowed to react with the corresponding propargylic alcohol HC≡CC(Me)R(OH) (R=Ph (A), c C4 H3 S (B), 4-MeS-C6 H4 (C), DMBT (D) or HC≡C-c C6 H10 (OH) (E) in the presence of TlBF4 and DBU to presumably give alkenylacetylide/allenylidene intermediates trans-[Ru{C≡CC(=CH2 )R}{C=C=C(Me)}(dppe)2 ]PF6 ([2]PF6 ). These complexes were not isolated but deprotonated to give the isolable bis(alkenylacetylide) complexes trans-[Ru{C≡CC(=CH2 )R}2 (dppe)2 ] (R=Ph (3 a), c C4 H3 S (3 b), 4-MeS-C6 H4 (3 c), DMBT (3 d)) and trans-[Ru{C≡C-c C6 H9 }2 (dppe)2 ] (3 e). Analogous reactions of trans-[Ru(CH3 )2 (dmpe)2 ], featuring the more electron-donating 1,2-bis(dimethylphosphino)ethane (dmpe) ancillary ligands, with the propargylic alcohols A or C and NH4 PF6 in methanol allowed isolation of the intermediate mixed alkenylacetylide/allenylidene complexes trans-[Ru{C≡CC(=CH2 )R}{C=C=C(Me)}(dmpe)2 ]PF6 (R=Ph ([4 a]PF6 ), 4-MeS-C6 H4 ([4 c]PF6 ). Deprotonation of [4 a]PF6 or [4 c]PF6 gave the symmetric bis(alkenylacetylide) complexes trans-[Ru{C≡CC(=CH2 )R}2 (dmpe)2 ] (R=Ph (5 a), 4-MeS-C6 H4 (5 c)), the first of their kind containing the dmpe ancillary ligand sphere. Attempts to isolate bis(allenylidene) complexes [Ru{C=C=C(Me)R}2 (PP)2 ]2+ (PP=dppe, dmpe) from treatment of the bis(alkenylacetylide) species 3 or 5 with HBF4 ⋅ Et2 O were ultimately unsuccessful.
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