Novel hexanuclear ruthenium clusters with unusual metal framework geometries: ‘boat’ and ‘sofa’ configurations of the Ru<sub>6</sub>core

Bodensieck, Ulf; Hoferkamp, Lisa; Stœckli-Evans, Helen; Süss-Fink, George

doi:10.1039/dt9930000127

Cited by 32 publications

(7 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The formation of 5 from thermolysis reactions of 1 in the presence of PPh 3 has interesting implications. The thermolysis of 1 in the absence of PPh 3 leads to an entirely different group of products …”

Section: Resultsmentioning

confidence: 99%

Reactions of the Trinuclear Cluster (μ₂-H)Ru₃(CO)₉(μ₃,η²-SCNHPhNPh): Synthesis and Molecular Structure of Ru₃(CO)₆(PPh₃)(μ₂,η²-C₆H₅)- (μ₂-PPh₂)(μ₃-S), a Complex Containing a Phenyl Ligand with a Rare σ,π-Coordination Mode

et al. 1996

Self Cite

View full text Add to dashboard Cite

Reactions of the previously isolated trinuclear cluster (μ2-H)Ru3(CO)9(μ3,η2-SCNHPhNPh) (1) with excess diphenylthiourea result in cluster fragmentation to produce the mononuclear complex Ru(CO)2(η2-SCNHPhNPh)2 (2) containing two bidentate diphenylthioureato ligands. Room-temperature reactions of 1 with 1 or 2 equiv of triphenylphosphine result in substitution of one or two carbonyl groups, respectively, to give the clusters (μ2-H)Ru3(CO)8(PPh3)(μ3,η2-SCNHPhNPh) (3) and (μ2-H)Ru3(CO)7(PPh3)2(μ3,η2-SCNHPhNPh) (4). An X-ray crystal structure analysis shows 3 to represent a monosubstituted derivative of 1 with the PPh3 ligand occupying an equatorial position on one of the two bridgehead ruthenium atoms; the crystal belongs to the triclinic space group P1̄; Z = 2, a = 10.014(2) Å, b = 14.449(4) Å, c = 14.573(4) Å, α = 100.38(2)°, β = 98.70(2)°, and γ = 107.20(2)°. Thermolysis of either 1 in the presence of 2 equiv of PPh3, or of 4 alone, gives the sulfur-capped, trinuclear cluster Ru3(CO)7(PPh3)(μ2,η2-C6H5)(μ2-PPh2)(μ3-S) (5). X-ray structural analysis of 5 shows a diphenylphosphido bridge and a phenyl bridge resulting from P−C bond activation of a PPh3 group and C−H activation of the aryl group; crystals of 5 are monoclinic, space group P21/n; Z = 4, a = 10.824(1) Å, b = 19.193(5) Å, c = 20.953(2) Å, and β = 97.44(1)°. Diphenylphosphinoethane (dppe) is found to replace two carbonyl ligands on two adjacent Ru atoms to give the cluster (μ2-H)Ru3(CO)7(Ph2PCH2CH2PPh2)- (μ3,η2-SCNHPhNPh) (6) whose X-ray structural analysis shows a dppe ligand bound cis to the μ2-S of the diphenylthioureato ligand and cis to the μ2-H ligand. Crystals of 6 are monoclinic, space group P21/n; Z = 4, a = 17.667(7) Å, b = 17.681(5) Å, c = 18.049(4) Å, and β = 108.06(2)°.

show abstract

Section: Resultsmentioning

confidence: 99%

Reactions of the Trinuclear Cluster (μ₂-H)Ru₃(CO)₉(μ₃,η²-SCNHPhNPh): Synthesis and Molecular Structure of Ru₃(CO)₆(PPh₃)(μ₂,η²-C₆H₅)- (μ₂-PPh₂)(μ₃-S), a Complex Containing a Phenyl Ligand with a Rare σ,π-Coordination Mode

et al. 1996

Self Cite

View full text Add to dashboard Cite

show abstract

“…L'assemblage conceptionnel de structures superieures a partir de structures de nuclkarite inferieure est encore assez limit(.. Adurns et collaborateurs ont dkmontri: l'utilitt de la presence de ligands auxiliaires ayant la capacitt: de ponter plusieurs atomes mktalliques, pour de telles reactions [l-51. Recemment nous avons publie la synthese de clusters hexanucliaires contenant une ossature mktallique en forme de bateau ou de divan, par condensation de deux unites trinucleaires [6]. Dans le present travail nous decrivons l'assemblage de clusters tetranucleaires a ossature planaire, a partir de deux unites dinucleaires.…”

unclassified

Construction de complexes tétranucléaires de ruthénium à ossature planaire par condensation de deux unités diruthénium à l'aide de ligands pontants: Synthèse et structure moléculaire de [Ru₄(CO)₈{μ₂‐P(Cy)₂}₄] et de [Ru₄(CO)₈{μ₄‐P(Cy)}₂{μ₂‐P(Cy)₂}₂] (Cy = cyclohexyl)

Béguin

Rheinwald

Stœckli-Evans

et al. 1994

Helvetica Chimica Acta

Self Cite

View full text Add to dashboard Cite

Assembly of Tetranuclear Ruthenium Complexes with Planar Metal Core by Condensation of Two Diruthenium Units Using Bridging Ligands: Synthesis and Molecular Structure of [Ru4(CO)8{μ2‐P(Cy)2}4] and [Ru4(CO)8{μ4‐P(Cy)}2{μ2}2](Cy = Cyclohexyl) The dinuclear complexes [Ru2(CO)6{μ‐P(Cy)2}2] (1) or [Ru2(CO)4{μ‐(HCO2)}2{P(Cy)2H}2] (2) react in THF solution at 160° to give the tetranuclear complexes [Ru4(CO)8{μ2‐P(Cy)2}4] (3) and [Ru4(CO)8{μ4‐P(Cy)}2{μ2‐P(Cy)2}2] (4), as well as the trinuclear complex [Ru3(CO)7(μ2‐H){μ2‐P(Cy)2}3] (5). If the reaction is performed at 200°, the bicapped tetranuclear species 4 is obtained in a higher yield, whereas 3 and 5 are formed in trace amounts only. The phenyl derivatives [Ru2(CO)6{μ‐P(Ph)2}2] (6) or [Ru2(CO)4{μ‐(EtCO2)}2{P(Ph)2H}2] (7) react in a similar manner to give only the complex [Ru4(CO)8{μ4‐P(Ph)}2{μ2‐P(Ph)2}2] (8), analogous to 4. The molecular structure of 3 consists of a planar framework of four Ru‐atoms, each Ru—Ru bond being bridged by a μ2‐dicyclohexylphosphino ligand. The complex 4 represents a planar rectangular Ru core, both faces being capped by μ4‐cyclohexylphosphinidene ligands and two opposite edges being bridged by μ2‐dicyclohexylphosphino ligands.

show abstract

“…The Ru-Ru bond distances within the basal plane span a wide range [2.787(2)−3.027(2) Å] with an apical Ru atom capped asymmetrically such that only two Ru(basal)−Ru(apex) bonds [Ru(3)−Ru(5) 2.787(1) Å and Ru(2)−Ru(5) 2.812(2) Å] are formed while the opposite edges [Ru(1)···Ru(5) 3.243(2) Å and Ru(4)···Ru(5) 3.181(2) Å] are significantly longer than the Ru−Ru metal bond found in [Ru 3 (CO) 12 ], indicating that there is no significant metal−metal bond between them. It is interesting to note that thermolysis of a related sulfur containing ruthenium cluster, [Ru 3 (CO) 9 (μ-H)(μ 3 -η 2 -PhNCSNHPh)] gives a μ 5 -sulfido complex [Ru 6 (CO) 16 (μ-H)(μ 5 -S)(μ 3 -η 2 -PhNCSNHPh)] …”

Section: Resultsmentioning

confidence: 99%

A Hexanuclear Ruthenium Carbonyl Cluster Containing both μ₃-Nitrene and μ₅-Nitrido Ligands

Lee

Wong

1996

Inorg. Chem.

View full text Add to dashboard Cite

show abstract

Novel hexanuclear ruthenium clusters with unusual metal framework geometries: ‘boat’ and ‘sofa’ configurations of the Ru₆core

Cited by 32 publications

References 19 publications

Reactions of the Trinuclear Cluster (μ₂-H)Ru₃(CO)₉(μ₃,η²-SCNHPhNPh): Synthesis and Molecular Structure of Ru₃(CO)₆(PPh₃)(μ₂,η²-C₆H₅)- (μ₂-PPh₂)(μ₃-S), a Complex Containing a Phenyl Ligand with a Rare σ,π-Coordination Mode

Reactions of the Trinuclear Cluster (μ₂-H)Ru₃(CO)₉(μ₃,η²-SCNHPhNPh): Synthesis and Molecular Structure of Ru₃(CO)₆(PPh₃)(μ₂,η²-C₆H₅)- (μ₂-PPh₂)(μ₃-S), a Complex Containing a Phenyl Ligand with a Rare σ,π-Coordination Mode

A Hexanuclear Ruthenium Carbonyl Cluster Containing both μ₃-Nitrene and μ₅-Nitrido Ligands

Contact Info

Product

Resources

About

Novel hexanuclear ruthenium clusters with unusual metal framework geometries: ‘boat’ and ‘sofa’ configurations of the Ru6core

Cited by 32 publications

References 19 publications

Reactions of the Trinuclear Cluster (μ2-H)Ru3(CO)9(μ3,η2-SCNHPhNPh): Synthesis and Molecular Structure of Ru3(CO)6(PPh3)(μ2,η2-C6H5)- (μ2-PPh2)(μ3-S), a Complex Containing a Phenyl Ligand with a Rare σ,π-Coordination Mode

Reactions of the Trinuclear Cluster (μ2-H)Ru3(CO)9(μ3,η2-SCNHPhNPh): Synthesis and Molecular Structure of Ru3(CO)6(PPh3)(μ2,η2-C6H5)- (μ2-PPh2)(μ3-S), a Complex Containing a Phenyl Ligand with a Rare σ,π-Coordination Mode

Construction de complexes tétranucléaires de ruthénium à ossature planaire par condensation de deux unités diruthénium à l'aide de ligands pontants: Synthèse et structure moléculaire de [Ru4(CO)8{μ2‐P(Cy)2}4] et de [Ru4(CO)8{μ4‐P(Cy)}2{μ2‐P(Cy)2}2] (Cy = cyclohexyl)

A Hexanuclear Ruthenium Carbonyl Cluster Containing both μ3-Nitrene and μ5-Nitrido Ligands

Contact Info

Product

Resources

About

Novel hexanuclear ruthenium clusters with unusual metal framework geometries: ‘boat’ and ‘sofa’ configurations of the Ru₆core

Reactions of the Trinuclear Cluster (μ₂-H)Ru₃(CO)₉(μ₃,η²-SCNHPhNPh): Synthesis and Molecular Structure of Ru₃(CO)₆(PPh₃)(μ₂,η²-C₆H₅)- (μ₂-PPh₂)(μ₃-S), a Complex Containing a Phenyl Ligand with a Rare σ,π-Coordination Mode

Reactions of the Trinuclear Cluster (μ₂-H)Ru₃(CO)₉(μ₃,η²-SCNHPhNPh): Synthesis and Molecular Structure of Ru₃(CO)₆(PPh₃)(μ₂,η²-C₆H₅)- (μ₂-PPh₂)(μ₃-S), a Complex Containing a Phenyl Ligand with a Rare σ,π-Coordination Mode

A Hexanuclear Ruthenium Carbonyl Cluster Containing both μ₃-Nitrene and μ₅-Nitrido Ligands