Formation of Cyclopentadienyl and Ruthenacyclopentadienyl Derivatives through Ynenyl-Diyne and Ynenyl-Alkyne Couplings onto a Triruthenium Cluster Core

The compound [Ru3(μ‐H)(μ3‐η2‐ampy)(CO)9] (1; Hampy=2‐amino‐6‐methylpyridine) reacts with diynes RC4R in THF at reflux temperature to give the ynenyl derivatives [Ru3(μ3‐η2‐ampy)(μ‐η3‐RC≡CC=CHR)(μ‐CO)2(CO)6] (2: R=CH2OPh; 3: R=Ph). These products contain a 1,4‐disubstituted butynen‐3‐yl ligand attach...

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Published in:Chemistry : a European journal 2001-06, Vol.7 (11), p.2370-2381
Main Authors: Cabeza, Javier A., del Río, Ignacio, García-Granda, Santiago, Lavigne, Guy, Lugan, Noël, Moreno, Marta, Nombel, Paul, Pérez-Priede, Mónica, Riera, Víctor, Rodríguez, Alejandra, Suárez, Marta, van der Maelen, Juan F.
Format: Article
Language:English
Subjects:
alkynes
cluster compounds
cycloaddition
diynes
ruthenium
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Summary:The compound [Ru3(μ‐H)(μ3‐η2‐ampy)(CO)9] (1; Hampy=2‐amino‐6‐methylpyridine) reacts with diynes RC4R in THF at reflux temperature to give the ynenyl derivatives [Ru3(μ3‐η2‐ampy)(μ‐η3‐RC≡CC=CHR)(μ‐CO)2(CO)6] (2: R=CH2OPh; 3: R=Ph). These products contain a 1,4‐disubstituted butynen‐3‐yl ligand attached to two ruthenium atoms. The compound [Ru3(μ‐η2‐ampy){μ3‐η6‐PhCC5(C≡CPh)HPh2}(CO)7] (4), which contains an η5‐cyclopentadienyl ring and a bridging carbene fragment, has also been obtained from the reaction of 1 with diphenylbutadiyne. This compound arises from a remarkable [3+2] cycloaddition reaction of a preformed 1,4‐diphenylbutynen‐4‐yl ligand with a triple bond of a second diphenylbutadiyne molecule. The reactivity of the ynenyl derivatives 2 and 3 with diynes and alkynes has been studied. In all cases, compounds of the general formula [Ru3(μ‐η2‐ampy){μ3‐η5‐C(=CHR)C=CRCR1=CR2}(CO)7] (5–17) have been obtained. They all contain a ruthenacyclopentadienyl fragment formed by coupling of the coordinated ynenyl ligand of 2 (R=CH2OPh) or 3 (R=Ph) with a triple bond of the new reagent (the CR1=CR2 fragment results from the incoming diyne or alkyne reagent). While most of the products derived from 2 have the alkenyl C=CHR fragment with a Z configuration (R cis to Ru), all the compounds obtained from 3 have this fragment with an E configuration. Except 2 and 3, all the cluster complexes described in this article have a five‐electron donor ampy ligand attached to only two metal atoms, a coordination mode unprecedented in cluster chemistry. The η5‐cyclopentadienyl complex A results from an unprecedented [3+2] cycloaddition reaction of a 1,4‐diphenylbutyn‐3‐en‐4‐yl ligand of a trinuclear cluster with a C≡C fragment of a diphenylbutadiyne molecule. Curiously, the reactions of diynes and alkynes with trinuclear clusters that contain 1,4‐disubstituted butyn‐3‐en‐3‐yl ligands lead to ruthenacyclopentadienyl derivatives of type B. In compounds A and B, the coordination of 2‐amidopyridine as a five‐electron‐donor μ‐η2‐ligand is unprecedented.
ISSN:0947-6539
1521-3765
DOI:10.1002/1521-3765(20010601)7:11<2370::AID-CHEM23700>3.0.CO;2-C