160758-93-0Relevant academic research and scientific papers
Ring-methyl activation in pentamethylcyclopentadienyl complexes. 4. Syntheses, structures, and reactions of [(C5Me4CH2Cl)RuCl(CO)2] and related compounds: X-ray structures of [(C5Me4CH2Cl)RuCl(CO)2] and [(C5Me4CH2OEt)Ru(PPh3)(CO) 2](OTf)
Fan, Li,Turner, Michael L.,Adams, Harry,Bailey, Neil A.,Maitlis, Peter M.
, p. 676 - 684 (1995)
The dicarbonyl chloro complex [(C5Me4CH2Cl)RuCl(CO)2] (4) is formed by carbonylation (1 atm, 20°C 5 min) of the dimeric tetramethylfulvene complex [{(C5Me4CH2)RuCl2}2] (3), which is in turn made by oxygenation (1 atm, 20°C, 30 min) of [{(C5Me5)RuCl2}2] (1); since both reactions proceed in high yield, 4 is a readily accessible starting material for a range of Cp*-substituted ruthenium complexes. The C-Cl in 4 is readily substituted by nucleophiles to give [(C5Me4CH2X)Ru(CO)2Cl] (X = OH, OMe, OEt, O-i-Pr, OPh, OCH2Ph, NEt2,H) and by PPh3 (in the presence of NH4PF6) to give [(C5Me4CH2PPh3)Ru(CO) 2Cl]PF6. The Ru-Cl in the alkoxy complexes [(C5Me4CH2OR)Ru(CO)2Cl] is replaced by reaction with KX to give [(C5Me4CH2OR)Ru(CO)2X] (R = Me, X = Br, I, CN, SCN; R = Et, X = Br, I) and by PPh3 in the presence of Ag+ to give [(C5Me4CH2OEt)Ru(CO)2(PPh 3)]+. Reaction of 4 with KCN or KSCN in MeOH gave a mixture of C(C5Me4CH2OMe)Ru(CO)2X], [(C5Me5)Ru(CO)2X], and [(C5Me4CH2X)Ru(CO)2X] (X = CN, SCN). The amines are quaternized; e.g., [(C5Me4-CH2NEt2)Ru(CO) 2Cl] reacted with MeI to give [(C5Me4CH2NEt2Me)Ru(CO) 2I]I. X-ray crystal structure determinations were carried out for [(C5Me4CH2Cl)Ru(CO)2Cl] (orthorhombic, a = 18.291(3) A?, b = 11.087(17) A?, c = 6.877(12) A?, V = 1394.6(4) A?3, Z = 4, Dc = 1.725 g cm-3, space group Pnma (D2h16, No. 62)) and [(C5Me4CH2OEt)Ru(CO)2(PPh 3)I+(OTf)- (triclinic, a = 10.496(12) A?, b = 12.509(9) A?, c = 12.738(7) A?, α = 90.25(5)°, β = 93.56(7)°, γ = 93.85(7)°, V = 1666(2) A?3, Z = 2, Dc = 1.491 g cm-3, space group P1 (Ci1 No. 2)).
