Synthesis and properties of carboxy-substituted half-sandwich ruthenium complexes with chelating bisphosphine ligands (η5-C5H4CO2H)Ru(η2-L)X (X=I, H)

Shaw, Anthony Peter Gordon; Guan, Huashi; Norton, Jack R.

doi:10.1016/j.jorganchem.2008.01.030

Cited by 12 publications

(8 citation statements)

References 37 publications

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“…The high symmetry of this arrangement results in only two resonances for the Cp hydrogens of the bisphosphine ligands (and only two resonances for the dppomf methyl groups of 4g + ). This argument has previously been made for 4f + and trans -(CpCO 2 H)Ru(dppf)(H) 2 + . , …”

Section: Resultssupporting

confidence: 54%

“…The anodic electrochemistry of free dppf, ,, dppomf, dippf, dppr, , dppo, , and dppc , has been reported. There are many reports of the electrochemical oxidation of complexes containing these and other metallocene-based bisphosphines. ,,,,− The oxidation of (Cp/Cp*)Ru complexes containing such ligands has not been studied extensively; the few chloride and hydride complexes that have been examined include CpRu(dppf)Cl ( 1a ), , Cp*Ru(dppf)Cl ( 1f ), CpRu(dppf)H ( 2a ), , Cp*Ru(dppf)H ( 2f ), ,, and the carboxy- and ester-substituted complexes (CpCO 2 H)Ru(dppf)Cl and (CpCO 2 t -Bu)Ru(dppf)Cl …”

Section: Resultsmentioning

confidence: 99%

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Synthesis, Electrochemistry, and Reactivity of Half-Sandwich Ruthenium Complexes Bearing Metallocene-Based Bisphosphines

Shaw¹,

Norton²,

Buccella³

et al. 2009

Organometallics

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The bimetallic complexes CpRu(P-P)X [Cp=η 5 -C 5 H 5 ; X=Cl, H; P-P=dppf (1,1 0 -bis(diphenylphosphino)ferrocene), dppr (1,1 0 -bis(diphenylphosphino)ruthenocene), dppo (1,1 0 -bis(diphenylphosphino)-osmocene), dippf (1,1 0 -bis(diisopropylphosphino)ferrocene), dcpf (1,1 0 -bis(dicyclohexylphosphino)ferrocene)], Cp*Ru(P-P)X [Cp*=η 5 -C 5 Me 5 ; X=Cl, H; P-P=dppf, dippf, dppomf (1,1 0 -bis(diphenylphosphino) octamethylferrocene), dppc (1,1 0 -bis(diphenylphosphino)cobaltocene)], [Cp*Ru(P-P)X] + (X=H, CCPh; P-P=dppc + ), and [Cp*Ru(P-P)L] 2+ (L= CH 3 CN, t-BuCN; P-P= dppc + ) have been synthesized. Most of the chloride and hydride complexes have been studied by cyclic voltammetry. The X-ray structures of [Cp*Ru(dppc)CH 3 CN][PF 6 ] 2 and [Cp*Ru(dppc)CCPh][PF 6 ] have been determined. Protonation of [Cp*Ru(dppc)CCPh] + gives the vinylidene complex [Cp*Ru(dppc)CCHPh] 2+ . The Co(III/II) potential of the dppc + ligand undergoes a cathodic shift upon coordination in [Cp*Ru-(dppc)H] + and an anodic shift upon coordination in [Cp*Ru(dppc)CH 3 CN] 2+ . The 1 H NMR spectrum of Cp*Ru(dppc)H is consistent with its formulation as a Co(II)/Ru(II) complex. As gauged by their reactivity toward iminium cations, the hydride complexes are poor hydride donors; proton and electron transfer are dominant. CpRu(dippf)H and CpRu(dcpf)H deprotonate iminium cations with acidic R-hydrogens. Cp*Ru(dppc)H is oxidized by the N-(benzylidene)pyrrolidinium cation, giving [Cp*Ru-(dppc)H] + and the vicinal diamine 1,2-bis(N-pyrrolidino)-1,2-diphenylethane. Most of the hydride complexes give trans-dihydride cations upon protonation; an exception is [Cp*Ru(dppc)H] + , which forms a dihydrogen complex [Cp*Ru(dppc)(H 2 )] 2+ with surprising kinetic stability. This dihydrogen complex is more acidic and less thermodynamically stable than its dihydride isomer. The H 2 ligand in [Cp*Ru(dppc)-(H 2 )] 2+ is readily replaced by nitriles; the reaction with t-BuCN occurs by a dissociative mechanism.

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Section: Resultssupporting

confidence: 54%

Section: Resultsmentioning

confidence: 99%

Synthesis, Electrochemistry, and Reactivity of Half-Sandwich Ruthenium Complexes Bearing Metallocene-Based Bisphosphines

Shaw¹,

Norton²,

Buccella³

et al. 2009

Organometallics

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“…The formerly singlet signal of the four aromatic protons appears as a pair of pseudo-triplets [27]. This kind of splitting is known and has been noted recently for related Cp R Ru(L 2 X) complexes [28].…”

Section: Synthesis and Characterization Of The Mixed Ligand Sandwich supporting

confidence: 60%

Ruthenium-based bioconjugates: Synthesis and X-ray structure of the mixed ligand sandwich compound RuCpiPr(p-(CO2H)C6H4Tp) and labelling of amino acids and the neuropeptide enkephalin

Zagermann

Kuchta

Merz

et al. 2009

Journal of Organometallic Chemistry

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“…As a result, the carboxylate anchor must be masked with a protecting group to avoid carboxylic acid intermediates. Our research group has focused primarily on the tert-butyl protecting group, because tbutyl esters are relatively stable and have well documented deprotection strategies under mild conditions (Jung & Lyster, 1977;Theodorou et al, 2018;Shaw et al, 2008). Herein, we report the synthesis, crystallization, and structural analysis of a t-butyl ester substituted titanocene dichloride that will serve as a convenient synthon for D--A titanocenes with carboxylate anchoring groups.…”

Section: Chemical Contextmentioning

confidence: 99%

“…Lithium tert-butyl ester cyclopentadienide (Shaw et al, 2008) (2.0278 g, 11.78 mmol, 1 eq) was dissolved by the addition of THF (15 mL) under an argon atmosphere. The reaction solution was chilled to 195 K and 1 M TiCl 4 solution in toluene (6 ml, 6 mmol, 0.5 eq) was added via syringe.…”

Section: Synthesis and Crystallizationmentioning

confidence: 99%

Synthesis and characterization of a tert-butyl ester-substituted titanocene dichloride: ^t-BuOOCCp₂TiCl₂

McCarthy¹,

McMillen²,

Pienkos³

et al. 2020

Acta Cryst E

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Bis[η5-(tert-butoxycarbonyl)cyclopentadienyl]dichloridotitanium(IV), [Ti(C10H13O2)2Cl2], was synthesized from LiCpCOOt-Bu using TiCl4, and was characterized by single-crystal X-ray diffraction and 1H NMR spectroscopy. The distorted tetrahedral geometry about the central titanium atom is relatively unchanged compared to Cp2TiCl2. The complex exhibits elongation of the titanium–cyclopentadienyl centroid distances [2.074 (3) and 2.070 (3) Å] and a contraction of the titanium–chlorine bond lengths [2.3222 (10) Å and 2.3423 (10) Å] relative to Cp2TiCl2. The dihedral angle formed by the planes of the Cp rings [52.56 (13)°] is smaller than seen in Cp2TiCl2. Both ester groups extend from the same side of the Cp rings, and occur on the same side of the complex as the chlorido ligands. The complex may serve as a convenient synthon for titanocene complexes with carboxylate anchoring groups for binding to metal oxide substrates.

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Synthesis and properties of carboxy-substituted half-sandwich ruthenium complexes with chelating bisphosphine ligands (η5-C5H4CO2H)Ru(η2-L)X (X=I, H)

Cited by 12 publications

References 37 publications

Synthesis, Electrochemistry, and Reactivity of Half-Sandwich Ruthenium Complexes Bearing Metallocene-Based Bisphosphines

Synthesis, Electrochemistry, and Reactivity of Half-Sandwich Ruthenium Complexes Bearing Metallocene-Based Bisphosphines

Ruthenium-based bioconjugates: Synthesis and X-ray structure of the mixed ligand sandwich compound RuCpiPr(p-(CO2H)C6H4Tp) and labelling of amino acids and the neuropeptide enkephalin

Synthesis and characterization of a tert-butyl ester-substituted titanocene dichloride: ^t-BuOOCCp₂TiCl₂

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Synthesis and properties of carboxy-substituted half-sandwich ruthenium complexes with chelating bisphosphine ligands (η5-C5H4CO2H)Ru(η2-L)X (X=I, H)

Cited by 12 publications

References 37 publications

Synthesis, Electrochemistry, and Reactivity of Half-Sandwich Ruthenium Complexes Bearing Metallocene-Based Bisphosphines

Synthesis, Electrochemistry, and Reactivity of Half-Sandwich Ruthenium Complexes Bearing Metallocene-Based Bisphosphines

Ruthenium-based bioconjugates: Synthesis and X-ray structure of the mixed ligand sandwich compound RuCpiPr(p-(CO2H)C6H4Tp) and labelling of amino acids and the neuropeptide enkephalin

Synthesis and characterization of a tert-butyl ester-substituted titanocene dichloride: t-BuOOCCp2TiCl2

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Synthesis and characterization of a tert-butyl ester-substituted titanocene dichloride: ^t-BuOOCCp₂TiCl₂