Study of the interaction of [Ru(C5H5)Cl(dippe)] and [Ru(C(5)Me(5))Cl(dippe)] with dihydrogen, dinitrogen, and other small molecules. X-ray crystal structures of [Ru(C(5)Me(5))H-2(dippe)][BPh(4)], [Ru(C5H5)(CNBu(t))(dippe)][BPh(4)], and [Ru(C5H5)(eta(2)-C2H4)(dippe)][BPh(4)]

The complexes [CpRuCl(dippe)] and [Cp*RuCl(dippe)] (Cp = C5H5; 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*RuH2(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 HBF4 . OEt(2) at low temperatures to give the dihydrogen adducts [CpRu(H-2)(dippe)][BF4] (5) and [Cp*Ru(H-2)(dippe)][BF4] (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(eta(6)-C(6)H(5)BPh(3))] (9) and (Pr2P)-Pr-i(O)CH2CH2P(O)Pr-i(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), C3H4 (13)), or [Cp*Ru(L)(dippe)][BPh(4)] (L = CO (14), CNBu(t) (15), C2H4 (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.