162443-13-2Relevant academic research and scientific papers
A Series of Rhodium(I) Complexes, including Carbene, Vinylidene and Allenylidene Derivatives, with the Bifunctional Arsine i-Pr2AsCH2CH2OMe as Ligand
Schwab, Peter,Werner, Helmut
, p. 3415 - 3426 (2007/10/02)
A series of rhodium(I) complexes containing the new bifunctional arsine ligand i-Pr2AsCH2CH2OMe I has been prepared.Most of the compounds were obtained from the ethane derivative trans- 5 which was obtained from 2> and I in about 80percent yield.The ethane can be displaced by CO, CN-t-Bu, CH2=CHC(O)Me, CH2=CHCO2Me, HCCPh, HCCCO2Me, PhCCSiMe3, MeCCMe, PhCCMe, MeCCCCMe or Me3SiCCCCSiMe3 (L) to give the four-co-ordinated rhodium(I) complexes trans- almost quantitatively.The reaction of 5 with H2 affords the dihydride which appears to be fluxional in solution.Photolysis of 5 leads to the elimination of CH2=CHOMe and the formation of trans- which is also accessible from 3 and HAsi-Pr2.The vinylidene complexes trans- are obtained either on photochemically induced rearrangement of the isomeric alk-1-yne derivatives (R = Ph or CO2Me) or directly from 5 and HCCR (R = Me or t-Bu).The reaction of 5 with a large excess of HCCMe or MeCC-t-Bu gives the rhodium(I) allenes trans- (R = H or t-Bu).The allenylidene compounds trans- (R = Ph, R' = Ph or C6H4Me-o) are obtained from the functionalized vinylidene derivatives trans- upon treatment with Al2O3.From trans- and NaC5H5 the half-sandwiches have been prepared.Compound 5 reacts with N2CPh2 and N2C(C6H4Me-p)2 to yield the carbene complexes trans- whereas from 5 and N2CRC(O)Ph (R = H or Ph) the diazoalkane rhodium compounds trans- (i-Pr2AsCH2CH2OMe)2> are obtained.
