The chemistry of tetraphenylcyclopentadienone complexes of ruthenium and rhodium: the X-ray crystal structure of [Ru{η5-C5Ph4OC(O)CH(OMe)Ph}(CO)2Cl]

Publisher Website
Google Scholar
Abstract
[Ru(η4-C5Ph4O)(CO)3](1) and [{Rh(η4-C5Ph4O)Cl}2](2) react with L-(–)-α-methylbenzylamine to give the tetraphenylcyclopentadienone complexes [Ru(η4-C5Ph4O)(CO)2{NH2CH(Me)Ph}] and [Rh(η4-C5Ph4O)Cl{NH2CH(Me)Ph}] respectively; trimethylamine N-oxide also reacts with complex (1) to give the amine adduct [Ru(η4-C5Ph4O)(CO)2(NMe3)](5). Complexes (2) and (5) oxidatively add HX to give the corresponding hydroxytetraphenylcyclopentadienyl complexes [{M(η5-C5Ph4OH)(L)X}n][M = Ru, L =(CO)2, X = Cl, OC(O)CF3, or OC(O)Me, n= 1; M = Rh, X = L = Cl, n= 2]; all these compounds readily reductively eliminate HX, the ease of this reaction increasing in the order of X and M listed. Methyl iodide also oxidatively adds to (5) to give the stable complex [Ru(η5-C5Ph4OMe)(CO)2I]. The acyl chlorides RC(O)Cl similarly oxidatively add to complexes (1) and (2) to give the corresponding ester complexes [M{η5-C5Ph4OC(O)R}(L)Cl}n][M = Ru, L =(CO)2, n= 1, R = Me; M = Rh, L = Cl, n= 2, R = Me or (–)CH(OMe)Ph]; the complex [Ru(η5-C5Ph4OH)(CO)2Cl] also reacts with RC(O)Cl to give [Ru{η5-C5Ph4OC(O)R}(CO)2Cl][R = Me or (–)CH(OMe)Ph (14)]. The X-ray structure of (14) is reported; the crystals are orthorhombic, space group p212121(no. 19) with a= 24.58(3), b= 14.518(13), c= 9.299(4)Å, and Z= 4. The structure was solved via the heavy-atom method and refined to R= 0.0541 using 1 425 independent reflections. Carbonylation of [{Rh(η5-C5Ph4OC(O)R*)Cl2}2] in the presence of zinc gives [Rh{η5-C5Ph4OC(O)R*}(CO)2] and complex (14) undergoes carbonyl substitution with triphenylphosphine to give the two diastereoisomers of [Ru{η5-C5Ph4OC(O)R*}(CO)(PPh3)Cl][R*=(–)CH(OMe)Ph]. The use of [Rh{η5-C5Ph4OC(O)R*}(CO)2] and [{Rh(η5-C5Ph4OC(O)R*}Cl2}2][R*=(–)CH(OMe)Ph] as asymmetric hydroformylation and hydrogenation catalysts respectively is briefly discussed. I.r., 1H, 13C, and 31P n.m.r. spectroscopic data are presented.

This publication has 0 references indexed in Scilit: