216588-82-8Relevant academic research and scientific papers
Addition of ethyl diazoacetate to the allenylidene ligand of [Ru(η5-C5H5)(C=C=CPh 2)(CO)(PPr3i)]BF4: Synthesis of ruthenium organometallic compounds containing new cyclic unsaturated η1-carbon ligands
Esteruelas, Miguel A.,Gómez, Angel V.,López, Ana M.,Carmen Puerta,Valerga, Pedro
, p. 4959 - 4965 (2008/10/08)
The allenylidene complex [Ru(η5-C5H5)(C=C=CPh 2)(CO)(PPr3i)]BF4 (1) reacts with ethyl diazoacetate to give the cyclic carbene derivative [Ru(η5-C5H5){=CCH=C(OEt)OC=CPh 2}(CO)(PPr3i)]BF4 (2). The structure of 2 was determined by an X-ray investigation, revealing a Ru-C distance of 2.017(6) A?. Treatment of 2 with sodium methoxide and methyllithium gives rise to the derivatives Ru(η5-C5H5){C=CHC(R)(OEt)OC=CPh 2}(CO)(PPr3i) (R = OMe (3), Me (4)). When a tetrahydrofuran solution of 3 is passed through an Al2O3 column, the lactonyl complex Ru(η5-C5H5){C=CHC(O)OC=CPh 2}(CO)(PPr3i) (5) is obtained. Complex 3 reacts with HBF4·OEt2 to regenerate 2 by selective elimination of methanol. The protonation of 4 with HBF4·OEt2 produces the elimination of ethanol and the formation of [Ru(η5-C5H5)-{=CCH=C(CH 3)OC=CPh2}(CO)(PPr3i)]BF4 (6). The structure of 6 was also determined by an X-ray investigation, revealing a Ru-C distance of 2.010(6) A?. The related cyclic carbene compound [Ru(η5-C5H5){=CCH=C(OH)OC=CPh 2}(CO)(PPr3i)]BF4 (7) has been prepared by reaction of 5 with HBF4-OEt2.
