Cyclohexadienyl derivatives of (ν6-arene) (hydrido tris(pyrazolyl) borato) ruthenium(II) compounds

Bhambri, Sameer; Tocher, Derek A.

doi:10.1016/0022-328x(95)06011-k

Cited by 21 publications

(10 citation statements)

References 13 publications

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“…C1 is, on average, twisted by 62.3° out of the arene plane. This expected conformational change by reduction/alkylation of the arene ligand has been observed in monoarene complexes of group 6 (Cr, Mo), group 7 (Mn, − Re − ), and group 8 (Fe, − Ru − ) elements, but rarely for bis-arene complexes . Crystallographic details for this and all subsequent structures are found in the Supporting Information Tables S1–S3.…”

Section: Resultsmentioning

confidence: 68%

Bis-Arene Complexes [Re(η⁶-arene)₂]⁺ as Highly Stable Bioorganometallic Scaffolds

et al. 2016

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The synthesis of mono- and difunctionalized [Re(η-CHR)(η-CHR)] (n = 0, 1; R = COOH, Br) complexes starting from [Re(η-benzene)] is described. The lithiation of [Re(η-benzene)] with n-BuLi leads preferentially to the neutral, alkylated product [Re(η-CH)(η-CH-Bu)] but not to the expected deprotonation of the arene ring. Deprotonation/lithiation with LDA gave the mono- and the dilithiated products in situ. Their reactions with 1,1,2,2-tetra-bromoethane (TBE) or with CO, respectively, gave [Re(η-CHBr)(η-CH)], [Re(η-CHBr)], or [Re(η-CHCOOH)(η-CH)], [Re(η-CHCOOH)]. These functionalized derivatives of [Re(η-benzene)] represent novel precursors for the synthesis of bioconjugates to bioactive structures, comparable to [Co(Cp)] or [Fe(Cp)]. Different model compounds [Re(η-CHR)(η-CHR)] (n = 0, 1; R = -SCHPh, -NHPh, -CONHCHPh, -CH-COdpa) were synthesized via amide bond formation and nucleophilic aromatic substitution. These conjugates were fully characterized including X-ray structure analyses of most products. For all complexes, the H NMR arene proton signals are strongly upfield-shifted as compared to those of the noncoordinated arenes. The electrochemical analyses show an irreversible, probably substituent-centered oxidation, which contrasts the cyclic voltammetry of the underivatized complexes where oxidation is fully reversible. The stability of the core and the reactivity of the substituents make these bis-arene complexes useful precursors in medicinal inorganic chemistry, comparable to cobaltocenium or ferrocene.

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Section: Resultsmentioning

confidence: 68%

Bis-Arene Complexes [Re(η⁶-arene)₂]⁺ as Highly Stable Bioorganometallic Scaffolds

et al. 2016

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“…The X‐ray structure of [(Et 2 PhP) 2 Ru(Cl){η 5 ‐C 6 H 6 (Me 3 SiP–P t Bu 2 )}] ( 1b ) is shown in Figure and the analogous X‐ray structure of 1c is presented in Figure S1 in the Supporting Information. Up to now, cases of structurally characterized cyclohexadienyl Ru II complexes have been limited to species with auxiliary tridentate chelate N ligands (σ/π donors) in a piano‐stool geometry . In 1b , the “piano‐stool” geometry is conserved, but Ru is coordinated to two σ‐donor/π‐acceptor P ligands and a chloride (σ/π donor) as well as the η 5 ‐cyclohexadienyl ligand.…”

Section: Resultsmentioning

confidence: 99%

“…Up to now, cases of structurally characterized cyclohexadienyl Ru II complexes have been limited to species with auxiliary tridentate chelate N ligands (σ/π donors) in a piano-stool geometry. [53][54][55][56][57] In 1b, the "piano-stool" geometry is conserved, but Ru is coordinated to two σ-donor/π-acceptor P ligands and a chloride (σ/π donor) as well as the η 5 -cyclohexadienyl ligand. It is evident that nucleophilic attack of the tBu 2 P-P(SiMe 3 ) moi-ety occurs through an exo pathway and results in a cyclohexadienyl ring with an envelope conformation.…”

Section: X-ray Structural Analysismentioning

confidence: 99%

Reactions of the Lithiated Diphosphine tBu₂P–P(SiMe₃)Li with [(η⁶‐C₆H₆)RuCl₂]₂ in the Presence of Tertiary Phosphines

Ponikiewski¹,

Kruczyński

Caporali

et al. 2016

Eur J Inorg Chem

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tBu2P–P(SiMe3)Li reacted with [(η6‐C6H6)RuCl2]2 at –40 °C in the presence of PR3 (PR3 = PEt3, PEt2Ph, PEtPh2) by the nucleophilic addition of the tBu2P–P(SiMe3) moiety to the benzene ring to yield solely the complexes [(R3P)2Ru(Cl){η5‐C6H6(Me3SiP–PtBu2)}] (1). These products decomposed slowly at ambient temperature to yield benzene, Ru clusters, and small amounts of the dinuclear ruthenium complexes [{(R3P)2Ru}2(µ,η2:2‐P2)2Ru(PR3)2] (Ru–Ru) (6). Single‐crystal X‐ray diffraction studies of [(PhEt2P)2Ru(Cl){η5‐C6H6(Me3SiP–PtBu2)}] (1b) and [(Ph2EtP)2Ru(Cl){η5‐C6H6(Me3SiP–PtBu2)}] (1c) revealed that the addition of the tBu2P–P(SiMe3) group occurred through an exo pathway. Complex 6a (R = Et) displays a planar rectangular P4 system consisting of two P2 units and a Ru–Ru distance that lies in the range of a single bond.

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“…The complexes which we have focused on are a selection of [Ru(η 6 -arene){κ 3 -HB(Pz 3 )}] ϩ and [Ru(η 6 -arene){κ 3 -HC-(Pz 3 )}] 2ϩ (Pz = pyrazol-1-yl) derivatives in which one might imagine that substituents in the '3' position on the pyrazolyl rings would interact with the π-bound arene to influence its reactivity. 10, 11 Preliminary results 12 indicated that while the interaction with the coordinated arene might be limited there is evidence of significant interaction in the cyclohexadienyl products formed by the attack of a single nucleophile. That interaction has now been extensively explored, is clearly a function of the substituents on the carbocyclic ring, and is the focus of this report.…”

Section: Introductionmentioning

confidence: 99%

“…Fig 12. Variation of the total EHMO energy of 9 as the cyclohexadienyl ring is rotated by 120Њ in steps of 6Њ, beginning in an eclipsed conformation.…”

mentioning

confidence: 99%

Synthesis, NMR studies, and molecular orbital calculations on cyclohexadienyl derivatives of (η6-arene)tris(pyrazolyl)ruthenium(II) compounds

Bhambri¹,

Bishop²,

Kaltsoyannis³

et al. 1998

J. Chem. Soc., Dalton Trans.

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Cyclohexadienyl derivatives of (ν6-arene) (hydrido tris(pyrazolyl) borato) ruthenium(II) compounds

Cited by 21 publications

References 13 publications

Bis-Arene Complexes [Re(η⁶-arene)₂]⁺ as Highly Stable Bioorganometallic Scaffolds

Bis-Arene Complexes [Re(η⁶-arene)₂]⁺ as Highly Stable Bioorganometallic Scaffolds

Reactions of the Lithiated Diphosphine tBu₂P–P(SiMe₃)Li with [(η⁶‐C₆H₆)RuCl₂]₂ in the Presence of Tertiary Phosphines

Synthesis, NMR studies, and molecular orbital calculations on cyclohexadienyl derivatives of (η6-arene)tris(pyrazolyl)ruthenium(II) compounds

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Cyclohexadienyl derivatives of (ν6-arene) (hydrido tris(pyrazolyl) borato) ruthenium(II) compounds

Cited by 21 publications

References 13 publications

Bis-Arene Complexes [Re(η6-arene)2]+ as Highly Stable Bioorganometallic Scaffolds

Bis-Arene Complexes [Re(η6-arene)2]+ as Highly Stable Bioorganometallic Scaffolds

Reactions of the Lithiated Diphosphine tBu2P–P(SiMe3)Li with [(η6‐C6H6)RuCl2]2 in the Presence of Tertiary Phosphines

Synthesis, NMR studies, and molecular orbital calculations on cyclohexadienyl derivatives of (η6-arene)tris(pyrazolyl)ruthenium(II) compounds

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Bis-Arene Complexes [Re(η⁶-arene)₂]⁺ as Highly Stable Bioorganometallic Scaffolds

Bis-Arene Complexes [Re(η⁶-arene)₂]⁺ as Highly Stable Bioorganometallic Scaffolds

Reactions of the Lithiated Diphosphine tBu₂P–P(SiMe₃)Li with [(η⁶‐C₆H₆)RuCl₂]₂ in the Presence of Tertiary Phosphines