The Chemistry of Tetraphenylcyclopentadienone Complexes of Ruthenium and Rhodium: the X-Ray Crystal Structure of 5-C5Ph4OC(O)CH(OMe)Ph>(CO)2Cl>

Article abstract of DOI:10.1039/DT9870002815

4-C5Ph4O)(CO)3> (1) and <4-C5Ph4O)Cl>2> (2) react with L-(-)-methylbenzylamine to give the tetraphenylcyclopentadienone complexes 4-C5Ph4O)(CO)2> and 4-C5Ph4O)Cl> respectively; trimethylamine N-oxide also reacts with complex (1) to give the amine adduct 4-C5Ph4O)(CO)2(NMe3)> (5).Complexes (2) and (5) oxidatively add HX to give the corresponding hydroxytetraphenylcyclopentadienyl complexes <5-C5Ph4OH)(L)X>n> ; all these compounds readily reductedively 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 5-C5Ph4OMe)(CO)2I>.The acyl chlorides RC(O)Cl similarly oxidatively add to complexes (1) and (2) to give the corresponding ester complexes 5-C5Ph4OC(O)R>(L)Cl>n> : the complex 5-C5Ph4OH)(CO)2Cl> also reacts with RC(O)Cl to give 5-C5Ph4OC(O)R>(CO)2Cl> .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) A, Z=4.The structure were solved via the heavy-atom method and refined to R=0.0541 using 1 425 independent reflections.Carbonylation of <5-C5Ph4OC(O)R^*)Cl2>2> in the presence of zinc gives 5-C5Ph4OC(O)R^*>(CO)2> and complex (14) undergoes carbonyl substitution with triphenylphosphine to give the two diastereoisomers of 5-C5Ph4OC(O)R^*>(CO)(PPh3)Cl> *=(-)CH(OMe)Ph>.The use of 5-C5Ph4OC(O)R^*>(CO)2> and 5-C5Ph4OC(O)R^*>Cl2>2> *=(-)CH(OMe)Ph> as asymmetric hydroformylation and hydrogenation catalysts respectively is briefly discussed.I.r., 1H, and 31P n.m.r. spectroscopic data are presented.