Synthesis, Structure, and Properties of a Tetrametallic Ferrocenecarboxylato-Bridged Copper(II) Complex

Costa, Ramon; López, Concepción; Molins, Elı́es; Espinosa, Enric

doi:10.1021/ic980409d

Cited by 39 publications

(21 citation statements)

References 38 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Less attention has been paid to the use of discrete dinuclear LM 2 complexes. To our knowledge, these complexes represent the fi rst class of compounds containing dinuclear aminethiolate complexes and redox-active ferrocenecarboxylates in the same molecule [72][73][74][75].…”

Section: Redox-active Ferrocenecarboxylates Anions Coordinated By Dinmentioning

confidence: 99%

“…Mold. 2013, 8 (1), [58][59][60][61][62][63][64][65][66][67][68][69][70][71][72][73][74][75][76][77] ) at 0.71 V, and iii) the oxidation of the thiophenolate sulfur atoms yielding a nickel bound thiyl radical at 1.59 V. Anodic shifts in the second and third redox waves are clearly discernible, confi rming the above fi ndings that the electron transfer events of the ferrocenyl moiety and the binuclear subunit infl uence one another. The fact that the potential shifts are not so pronounced than in 9 is in good agreement with the smaller positive charges of the participating species.…”

Section: Scheme 5 Assignment Of Redox Processes In 9-11 and 14mentioning

confidence: 99%

See 1 more Smart Citation

Dinuclear Complexes as Building Blocks for Tetra-Nuclear Macrocyclic Complexes with Dithiolate Macrocyclic Ligand

Lozan¹

2013

ChemJMold

View full text Add to dashboard Cite

A series of novel tri-, tetra-and pentanuclear complexes composed of dinuclear LM 2 units (M=Co, Ni, Zn; L=24-membered macrocyclic hexaaza-dithiophenolate ligand) and ferrocene-carboxylate ([CpFeC 5 H 4 CO 2 ]ˉ), 1,1'-ferro-cenedicarboxylate ([Fe(C 5 Keywords: coordination chemistry, amino-thiophenolate ligands, di-and tetranuclear complexes, ferrocene and naphthalene diimide derivatives, polynuclear complexes IntroductionThe chemistry of container molecules has developed extensively over the past two decades. Many container molecules such as calixarenes, resorcarenes, cyclodextrins, carcerands and glycourils have been invaluable in studying the fundamental principles of inclusion phenomena and consequently their use in separation science or drug delivery, as two examples of application. Importantly, the area has attracted interest in the field of supramolecular chemistry because the properties of such host-guest compounds are often different from those of their constituent components. By adjusting the size and form of the binding cavity it is often possible to complex co-ligands in unusual coordination modes, to activate and transform small molecules, or to stabilize reactive intermediates [1,2]. One subclass are the metallated container molecules, in which metal ions and clusters are used as both a point of recognition and to give the container a well-defined structure. Such compounds also allow for an interplay of molecular recognition and transition-metal catalysis, and for the construction of more effective enzyme mimics. Of interest to the present work is the ability of metallocavitands to recognize and encapsulate difunctionalised molecules towards stabilising or enhancing the optical and electronic properties of redox-and photo-active compounds within a confined environment set up by two hemispheres.The carboxylate group, RCO 2-, can bind to transition metals in a variety of coordination modes giving rise to complexes of great structural diversity [3]. Current activities focus on the coordination chemistry of polycarboxylate ligands, as these offer great potential in the construction of polynuclear aggregates [4] and extended coordination polymers with micro-and mesoporous structures [5][6][7][8] or catalytic properties [9]. In addition, polycarboxylate ligands are of importance as spin-coupling bridging ligands [10][11][12][13][14][15][16][17] in the rapidly expanding fi eld of molecular magnetism [18, 19]. In this context, an enormous amount of literature has been generated concerning the distance dependence of magnetic exchange interactions between metal atoms linked by extended dicarboxylate ligands. Dinuclear copper complexes bridged by oxalate [20, 21] and terephthalate [22][23][24] dianions form, by far, the largest group of such systems, and it appears that the exchange interactions depend on the M···M distance [25], the relative orientation of the magnetic orbitals [26], and the degree of conjugation of the organic spacer unit [27, 28].

show abstract

Section: Redox-active Ferrocenecarboxylates Anions Coordinated By Dinmentioning

confidence: 99%

Section: Scheme 5 Assignment Of Redox Processes In 9-11 and 14mentioning

confidence: 99%

Dinuclear Complexes as Building Blocks for Tetra-Nuclear Macrocyclic Complexes with Dithiolate Macrocyclic Ligand

Lozan¹

2013

ChemJMold

View full text Add to dashboard Cite

show abstract

“…The incorporation of metallo ligands into coordination polymers is still rare. [25][26][27][28][29][30][31][32][33] In this context we became interested in using (benzoic acid)tricarbonylchromium as a starting material [5,6] for the construction of oligomeric and polymeric materials. Our intention was to study the influence of the organometallic compound on the formation process and on the structures of the coordination compounds in a systematic way.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Structures of Cadmium(II) Complexes with (η⁶‐Benzenecarboxylate)tricarbonylchromium

Murugesapandian

Roesky

2011

Eur J Inorg Chem

View full text Add to dashboard Cite

The reaction of (benzoic acid)tricarbonylchromium [(η6‐C6H5COOH)Cr(CO)3] with cadmium acetate in methanol or DMF led to the formation of the dinuclear cadmium compounds [Cd2{(η6‐C6H5COO)Cr(CO)3}4(MeOH)4] (1) or [Cd2{(η6‐C6H5COO)Cr(CO)3}4(DMF)4] (2) containing four organometallic ligands with four methanol or DMF molecules coordinated to the cadmium atoms. The reaction of (benzoic acid)tricarbonylchromium [(η6‐C6H5COOH)Cr(CO)3] and cadmium acetate with 1,10‐phenanthroline (1,10‐phen) afforded the dinuclear cadmium complex [Cd2{(η6‐C6H5COO)Cr(CO)3}4(1,10‐phen)2] (3) with two 1,10‐phenanthroline and four organometallic ligands. The reaction of (benzoic acid)tricarbonylchromium [(η6‐C6H5COOH)Cr(CO)3] with cadmium acetate in the presence of 4,4′‐bipyridine (4,4′‐bipy) led to the one‐dimensional coordination polymer [Cd2{(η6‐C6H5COO)Cr(CO)3}4(4,4′‐bipy)2·3DMF]n (4) containing a dinuclear cadmium complex as a repeating unit. The solid‐state structures of all the compounds were determined by single‐crystal X‐ray diffraction.

show abstract

“…To our knowledge, these complexes represent the first class of compounds containing dinuclear aminethiolate complexes and redox-active ferrocenecarboxylates in the same molecule. [26][27][28] Results and Discussion Syntheses and characterization: It was our aim to synthesize polynuclear complexes containing classical and organometallic complex fragments. Two types of complexes were considered: trinuclear [LM The trinuclear Co 2 Fe and Ni 2 Fe complexes, 6 and 7, were obtained in almost quantitative yield by reaction of the corresponding chloride complex [LM 2 …”

Section: Introductionmentioning

confidence: 99%

Dinuclear Amine–Thiophenolate Complexes Coligated by Ferrocenemonocarboxylate and 1,1′‐Ferrocenedicarboxylate Anions: Preparation, Characterization and Structures of Trinuclear [LM^II₂(O₂CC₅H₄FeCp)]⁺ and Pentanuclear [(LM^II₂)₂(O₂CC₅H₄)₂Fe]²⁺ Complexes (M=Co, Ni, Zn)

Lozan

Buchholz

Plass

et al. 2007

Chemistry A European J

View full text Add to dashboard Cite

A series of novel tri- and pentanuclear complexes composed of dinuclear LM(2) units (M=Co, Ni, Zn; L=24-membered macrocyclic hexaazadithiophenolate ligand) and ferrocenecarboxylate ([CpFeC(5)H(4)CO(2)](-)) or 1,1'-ferrocenedicarboxylate ([Fe(C(5)H(4)CO(2))(2)](2-)) groups is reported. The complexes [LM(II) (2)(O(2)CC(5)H(4)FeCp)](+) (M=Co (6), Ni (7), Zn (8)) and [(LM(II) (2))(2)(O(2)CC(5)H(4))(2)Fe](2+) (M=Co (9), Ni (10)) have been prepared by substitution reactions from labile [LM(II) (2)L'](+) precursors (L'=Cl, OAc) and the respective ferrocenecarboxylate anions in methanol. Mixed-valent [(LCo(II)Co(III))(2)(O(2)CC(5)H(4))(2)Fe](4+) (11) was prepared by oxidation of 9 with bromine. Complexes 7[BPh(4)], 8[BPh(4)], 9[BPh(4)](2), 10[BPh(4)](2), and 11[ClO(4)](4) have been characterized by X-ray crystallography; showing that the ferrocenyl carboxylates act as bidentate (7, 8) or bis-bidentate (9-11) bridging ligands towards one or two bioctahedral LM(2) subunits, respectively. The structures are retained in solution as indicated by NMR spectroscopic studies on the diamagnetic Zn(2)Fe complex 8[ClO(4)]. Electrochemical studies reveal significant anodic potential shifts for the oxidation potential of the ferrocenyl moieties upon complexation and the magnitude of the potential shift appears to correlate with the charge of the LM(2) subunits. This is qualitatively explained in terms of destabilizing electrostatic (Coulomb) interactions between the M(2+) ions of the LM(2) unit and the proximate ferrocenium fragment. An analysis of the temperature-dependent magnetic susceptibility data for 10[BPh(4)](2) shows the presence of weak ferromagnetic magnetic exchange interactions between the Ni(II) ions in the LNi(2) units. The exchange coupling across the ferrocenedicarboxylate bridge is negligible.

show abstract

Synthesis, Structure, and Properties of a Tetrametallic Ferrocenecarboxylato-Bridged Copper(II) Complex

Cited by 39 publications

References 38 publications

Dinuclear Complexes as Building Blocks for Tetra-Nuclear Macrocyclic Complexes with Dithiolate Macrocyclic Ligand

Dinuclear Complexes as Building Blocks for Tetra-Nuclear Macrocyclic Complexes with Dithiolate Macrocyclic Ligand

Synthesis and Structures of Cadmium(II) Complexes with (η⁶‐Benzenecarboxylate)tricarbonylchromium

Dinuclear Amine–Thiophenolate Complexes Coligated by Ferrocenemonocarboxylate and 1,1′‐Ferrocenedicarboxylate Anions: Preparation, Characterization and Structures of Trinuclear [LM^II₂(O₂CC₅H₄FeCp)]⁺ and Pentanuclear [(LM^II₂)₂(O₂CC₅H₄)₂Fe]²⁺ Complexes (M=Co, Ni, Zn)

Contact Info

Product

Resources

About

Synthesis, Structure, and Properties of a Tetrametallic Ferrocenecarboxylato-Bridged Copper(II) Complex

Cited by 39 publications

References 38 publications

Dinuclear Complexes as Building Blocks for Tetra-Nuclear Macrocyclic Complexes with Dithiolate Macrocyclic Ligand

Dinuclear Complexes as Building Blocks for Tetra-Nuclear Macrocyclic Complexes with Dithiolate Macrocyclic Ligand

Synthesis and Structures of Cadmium(II) Complexes with (η6‐Benzenecarboxylate)tricarbonylchromium

Dinuclear Amine–Thiophenolate Complexes Coligated by Ferrocenemonocarboxylate and 1,1′‐Ferrocenedicarboxylate Anions: Preparation, Characterization and Structures of Trinuclear [LMII2(O2CC5H4FeCp)]+ and Pentanuclear [(LMII2)2(O2CC5H4)2Fe]2+ Complexes (M=Co, Ni, Zn)

Contact Info

Product

Resources

About

Synthesis and Structures of Cadmium(II) Complexes with (η⁶‐Benzenecarboxylate)tricarbonylchromium

Dinuclear Amine–Thiophenolate Complexes Coligated by Ferrocenemonocarboxylate and 1,1′‐Ferrocenedicarboxylate Anions: Preparation, Characterization and Structures of Trinuclear [LM^II₂(O₂CC₅H₄FeCp)]⁺ and Pentanuclear [(LM^II₂)₂(O₂CC₅H₄)₂Fe]²⁺ Complexes (M=Co, Ni, Zn)