(tert-Butyl isocyano-C)(carbonyl)(η5-cyclopentadienyl)(triphenylphosphine-P)ruthenium(II) hexafluorophosphate

Simpson, Stephen J.

doi:10.1107/s0108270193000733

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“…These two observations are frequent for complexes containing CNBu t ligands . The C(20)−N and N−C(21) separations of 1.148(9) and 1.48(1) Å, respectively, compare well with those found in other half-sandwich ruthenium isocyanide complexes, i.e., [CpRuI(CNBu t ) 2 ] (1.159 and 1.442 Å) and [CpRu(CNBu t )(CO)(PPh 3 )][PF 6 ] (1.152 and1.460 Å) . These bond distances do not differ much from those found in the free isocyanide, suggesting that there is very little back-bonding from the metal.…”

Section: Resultssupporting

confidence: 67%

Study of the Interaction of [Ru(C₅H₅)Cl(dippe)] and [Ru(C₅Me₅)Cl(dippe)] with Dihydrogen, Dinitrogen, and Other Small Molecules. X-ray Crystal Structures of [Ru(C₅Me₅)H₂(dippe)][BPh₄], [Ru(C₅H₅)(CNBu^t)(dippe)][BPh₄], and [Ru(C₅H₅)(η²-C₂H₄)(dippe)][BPh₄]

et al. 1996

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The complexes [CpRuCl(dippe)] and [Cp*RuCl(dippe)] (Cp = C5H5; Cp* = C5Me5; dippe = 1,2-bis(diisopropylphosphino)ethane) react with H2 and Na[BPh4] in EtOH or MeOH to furnish the dihydrides [CpRuH2(dippe)][BPh4] (1) and [Cp*RuH2(dippe)][BPh4] (2). These compounds are deprotonated by KOBut to yield the monohydrides [CpRuH(dippe)] (3) and [Cp*RuH(dippe)] (4), which can be protonated back by HBF4·OEt2 at low temperatures to give the dihydrogen adducts [CpRu(H2)(dippe)][BF4] (5) and [Cp*Ru(H2)(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(N2)(dippe)][BPh4] (7) and the acetone adduct [CpRu(Me2CO)(dippe)][BPh4] (8) were obtained by reaction of [CpRuCl(dippe)] with Ag+ in acetone under dinitrogen or argon, respectively, followed by NaBPh4/EtOH. Both compounds react with atmospheric oxygen yielding [CpRu(η6-C6H5BPh3)] (9) and iPr2P(O)CH2CH2P(O)iPr2. The dinitrogen adduct [Cp*Ru(N2)(dippe)][BPh4] (10) was also obtained, but it reacts irreversibly with traces of O2 to give the dioxygen complex [Cp*Ru(O2)(dippe)][BPh4], previously known. A range of neutral donors L also react with [CpRuCl(dippe)] or [Cp*RuCl(dippe)] and NaBPh4 furnishing the corresponding complexes [CpRu(L)(dippe)][BPh4] (L = CO (11), CNBut (12), C2H4 (13)), or [Cp*Ru(L)(dippe)][BPh4] (L = CO (14), CNBut (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.

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Section: Resultssupporting

confidence: 67%

Study of the Interaction of [Ru(C₅H₅)Cl(dippe)] and [Ru(C₅Me₅)Cl(dippe)] with Dihydrogen, Dinitrogen, and Other Small Molecules. X-ray Crystal Structures of [Ru(C₅Me₅)H₂(dippe)][BPh₄], [Ru(C₅H₅)(CNBu^t)(dippe)][BPh₄], and [Ru(C₅H₅)(η²-C₂H₄)(dippe)][BPh₄]

et al. 1996

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(tert-Butyl isocyano-C)(carbonyl)(η5-cyclopentadienyl)(triphenylphosphine-P)ruthenium(II) hexafluorophosphate

Abstract: The crystal structure of the title compound consists of discrete [Ru(CWBu)(CO)(PPh3)(r/5-CsHs)] ÷ cations and [PF6]-anions. The cation has pseudooctahedral symmetry with the cyclopentadienyl group occupying three sites in a facial arrangement. Comment

Cited by 1 publication

References 4 publications

Study of the Interaction of [Ru(C₅H₅)Cl(dippe)] and [Ru(C₅Me₅)Cl(dippe)] with Dihydrogen, Dinitrogen, and Other Small Molecules. X-ray Crystal Structures of [Ru(C₅Me₅)H₂(dippe)][BPh₄], [Ru(C₅H₅)(CNBu^t)(dippe)][BPh₄], and [Ru(C₅H₅)(η²-C₂H₄)(dippe)][BPh₄]

Study of the Interaction of [Ru(C₅H₅)Cl(dippe)] and [Ru(C₅Me₅)Cl(dippe)] with Dihydrogen, Dinitrogen, and Other Small Molecules. X-ray Crystal Structures of [Ru(C₅Me₅)H₂(dippe)][BPh₄], [Ru(C₅H₅)(CNBu^t)(dippe)][BPh₄], and [Ru(C₅H₅)(η²-C₂H₄)(dippe)][BPh₄]

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(tert-Butyl isocyano-C)(carbonyl)(η5-cyclopentadienyl)(triphenylphosphine-P)ruthenium(II) hexafluorophosphate

Abstract: The crystal structure of the title compound consists of discrete [Ru(CWBu)(CO)(PPh3)(r/5-CsHs)] ÷ cations and [PF6]-anions. The cation has pseudooctahedral symmetry with the cyclopentadienyl group occupying three sites in a facial arrangement. Comment

Cited by 1 publication

References 4 publications

Study of the Interaction of [Ru(C5H5)Cl(dippe)] and [Ru(C5Me5)Cl(dippe)] with Dihydrogen, Dinitrogen, and Other Small Molecules. X-ray Crystal Structures of [Ru(C5Me5)H2(dippe)][BPh4], [Ru(C5H5)(CNBut)(dippe)][BPh4], and [Ru(C5H5)(η2-C2H4)(dippe)][BPh4]

Study of the Interaction of [Ru(C5H5)Cl(dippe)] and [Ru(C5Me5)Cl(dippe)] with Dihydrogen, Dinitrogen, and Other Small Molecules. X-ray Crystal Structures of [Ru(C5Me5)H2(dippe)][BPh4], [Ru(C5H5)(CNBut)(dippe)][BPh4], and [Ru(C5H5)(η2-C2H4)(dippe)][BPh4]

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Study of the Interaction of [Ru(C₅H₅)Cl(dippe)] and [Ru(C₅Me₅)Cl(dippe)] with Dihydrogen, Dinitrogen, and Other Small Molecules. X-ray Crystal Structures of [Ru(C₅Me₅)H₂(dippe)][BPh₄], [Ru(C₅H₅)(CNBu^t)(dippe)][BPh₄], and [Ru(C₅H₅)(η²-C₂H₄)(dippe)][BPh₄]

Study of the Interaction of [Ru(C₅H₅)Cl(dippe)] and [Ru(C₅Me₅)Cl(dippe)] with Dihydrogen, Dinitrogen, and Other Small Molecules. X-ray Crystal Structures of [Ru(C₅Me₅)H₂(dippe)][BPh₄], [Ru(C₅H₅)(CNBu^t)(dippe)][BPh₄], and [Ru(C₅H₅)(η²-C₂H₄)(dippe)][BPh₄]