The complexes [CpRuCl(dippe)] and [Cp*RuCl(dippe)] (Cp = C 5 H 5; Cp* = C 5 Me 5; dippe = 1,2-bis(diisopropylphosphino)ethane) react with H 2 and Na[BPh 4 ] in EtOH or MeOH to furnish the dihydrides [CpRuH 2 (dippe)][BPh 4 ] ( 1 ) and [Cp*RuH 2 (dippe)][BPh 4 ] ( 2 ). These compounds are deprotonated by KOBu t to yield the monohydrides [CpRuH(dippe)] ( 3 ) and [Cp*RuH(dippe)] ( 4 ), which can be protonated back by HBF 4 ·OEt 2 at low temperatures to give the dihydrogen adducts [CpRu(H 2 )(dippe)][BF 4 ] ( 5 ) and [Cp*Ru(H 2 )(dippe)][BF 4 ] ( 6 ). These compounds rearrange irreversibly to the dihydride form as the temperature is raised. A kinetic study of these rearrangement processes suggests that the isomerization mechanism is different in each case. The dinitrogen complex [CpRu(N 2 )(dippe)][BPh 4 ] ( 7 ) and the acetone adduct [CpRu(Me 2 CO)(dippe)][BPh 4 ] ( 8 ) were obtained by reaction of [CpRuCl(dippe)] with Ag + in acetone under dinitrogen or argon, respectively, followed by NaBPh 4 /EtOH. Both compounds react with atmospheric oxygen yielding [CpRu(η 6 -C 6 H 5 BPh 3 )] ( 9 ) and i Pr 2 P(O)CH 2 CH 2 P(O) i Pr 2 . The dinitrogen adduct [Cp*Ru(N 2 )(dippe)][BPh 4 ] ( 10 ) was also obtained, but it reacts irreversibly with traces of O 2 to give the dioxygen complex [Cp*Ru(O 2 )(dippe)][BPh 4 ], previously known. A range of neutral donors L also react with [CpRuCl(dippe)] or [Cp*RuCl(dippe)] and NaBPh 4 furnishing the corresponding complexes [CpRu(L)(dippe)][BPh 4 ] (L = CO ( 11 ), CNBu t ( 12 ), C 2 H 4 ( 13 )), or [Cp*Ru(L)(dippe)][BPh 4 ] (L = CO ( 14 ), CNBu t ( 15 ), C 2 H 4 ( 16 )). The ethylene adduct 16 is only stable under an ethylene atmosphere, whereas 13 is a stable species. The X-ray crystal structures of compounds 2, 12, and 13 are also reported.
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Rios et al. (1996) studied this question.
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