Elemental Carbon Chain Bridging Two Iron Centers: Syntheses and Spectroscopic Properties of [Cp*(dppe)Fe-C4-FeCp*(dppe)]n+.cntdot.n[PF6]-. X-ray Crystal Structure of the Mixed Valence Complex (n = 1)

Narvor, Nathalie Le; Toupet, L.; Lapinte, Claude

doi:10.1021/ja00132a013

Cited by 435 publications

(338 citation statements)

References 3 publications

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“…[9] The two currently most popular classes of ligands that promote coupling in bimetallic systems are comprised of either ditopic bi-and oligopyridines, [10] and of oliogacetylenes. [11] While the latter type of ligands offers an excellent electronic link between the metal and the bridging ligand with a high degree of d M -p L overlap, especially in metal-alkylidene and metal-alkynylidene oxidation states, the oligopyridine family dwells on the p-acidity of the chelating pyridyl ligand and its synthetic versatility for functionalization. In a simplistic view, N-heterocyclic carbenes (NHCs) [12] represent a fusion of these two successful classes of ligands, featuring the synthetic versatility [13] of pyridines with the (partial) p component of the M À C NHC bond [14] reminiscent of acetylenes.…”

Section: Introductionmentioning

confidence: 99%

Efficient Electronic Communication of Two Ruthenium Centers through a Rigid Ditopic N‐Heterocyclic Carbene Linker

Nussbaum

Schuster

Albrecht

2013

Chemistry A European J

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A ditopic benzobis(carbene) ligand precursor was prepared that contained a chelating pyridyl moiety to ensure co‐planarity of the carbene ligand and the coordination plane of a bound octahedral metal center. Bimetallic ruthenium complexes comprising this ditopic ligand [L4Ru‐C,N‐bbi‐C,N‐RuL4] were obtained by a transmetalation methodology (C,N‐bbi‐C,N=benzobis(N‐pyridyl‐N′‐methyl‐imidazolylidene). The two metal centers are electronically decoupled when the ruthenium is in a pseudotetrahedral geometry imparted by a cymene spectator ligand (L4=[(cym)Cl]). Ligand exchange of the Cl−/cymene ligands for two bipyridine or four MeCN ligands induced a change of the coordination geometry to octahedral. As a consequence, the ruthenium centers, separated through space by more than 10 Å, become electronically coupled, which is evidenced by two distinctly different metal‐centered oxidation processes that are separated by 134 mV (L4=[(bpy)2]; bpy=2,2′‐bipyridine) and 244 mV (L4=[(MeCN)4]), respectively. Hush analysis of the intervalence charge‐transfer bands in the mixed‐valent species indicates substantial valence delocalization in both complexes (delocalization parameter Γ=0.41 and 0.37 in the bpy and MeCN complexes, respectively). Spectroelectrochemical measurements further indicated that the mixed‐valent RuII/RuIII species and the fully oxidized RuIII/RuIII complexes gradually decompose when bound to MeCN ligands, whereas the bpy spectators significantly enhance the stability. These results demonstrate the efficiency of carbenes and, in particular, of the bbi ligand scaffold for mediating electron transfer and for the fabrication of molecular redox switches. Moreover, the relevance of spectator ligands is emphasized for tailoring the degree of electronic communication through the benzobis(carbene) linker.

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Section: Introductionmentioning

confidence: 99%

Efficient Electronic Communication of Two Ruthenium Centers through a Rigid Ditopic N‐Heterocyclic Carbene Linker

Nussbaum

Schuster

Albrecht

2013

Chemistry A European J

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“…The one-dimensional-C 4 -bridge acts as a molecular wire to convey the odd electron from one metal center to the other. The high value of ∆E p = 720 V, corresponding to a K C = 1.60 x 10 12 , reported for complex ([FeCp*(dppe)]-C≡C-C≡C-[FeCp*(dppe)]) 11 , shows that the delocalization, greatly favored by the -C x -bridge, strongly depends on the electronic structure of the metal unit. Figure 4 shows the cyclic voltammetric response for complex 1, synthesized using bis(trimethylsilyl) acetylene as the ligand.…”

Section: Cyclic Voltammetric Analysis Of [Cis-{rucl (Bpy) 2 (M-c≡c-)}mentioning

confidence: 94%

Synthesis and electrochemical characterization of bimetallic ruthenium complexes with the bridging eta2(<FONT FACE=Symbol>s,s</FONT>)-1,3-butadiyne-1,4-diyl ligand

Stein¹,

Oki²,

Vichi³

2000

J. Braz. Chem. Soc.

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ºC-)}] 2 (1) foi obtido pelo tratamento de 1 equive de 1,4-bis(trimetilsilil)-1,3-butadiino ou bis(trimetilsilil)acetileno com 2 equiv do complexo cis-[RuCl2(bpy)2].2H2O, NaF e NaBF4na mistura de solventes metanol/CH2Cl2 (10/1) com rendimentos de 52% e 35%, respectivamente. Análises de RMN de ¹H, 13C{H} e principalmente eletroquímica, confirmaram que o mesmo produto foi obtido dos dois métodos. Análise de (1) através de voltametria cíclica, no intervalo de potencial de 0 a 1,20 V mostrou dois picos de oxidação quasi-reversíveis referentes ao par redox Ru(II)/Ru(III). Os dois processos redox são separados por 520 V, indicando comunicação eletrônica significante entre os dois centros metálicos]]>

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“…[1][2][3][4][5][6][7] This interest is justified, owing to the need for novel functional materials with technological applications. Such supramolecular systems possess functionality that makes them attractive for a number of potential applications, including molecular wires, [8][9][10][11][12][13] catalysts, [14] chemical sensors, [15,16] photoluminescence materials, [17] and molecular magnets. [18] To date, most of these supramolecular species self-assemble by combination of metal ions of different coordination geometries and a variety of organic bridging ligands.…”

Section: Introductionmentioning

confidence: 99%

Supramolecular Assemblies Based on Organometallic Quinonoid Linkers: A New Class of Coordination Networks

Moussa¹,

Amouri²

2008

Angew Chem Int Ed

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Self-assembly of coordination frameworks exhibiting original architectures is an active area of research. Generally, such assemblies are constructed from organic spacers and transition metals of different geometrical structures. Herein, we report a novel class of supramolecular coordination assemblies with organometallic linkers based on metalated quinonoid and thioquinonoid complexes that serve as spacers. The organometallic ligands are stable and have the general formula [Cp*M(eta(4)-benzoquinone)] (o- and p-benzoquinone, Cp*=C(5)Me(5), M=Rh, Ir) and [Cp*Ir(eta(4)-thiobenzoquinone)] (o- and p-thiobenzoquinone). These units bind through both oxygen or sulfur atoms to metal ions of different coordination geometry, such as Cu(I), Ag(I), and Pt(II), to generate supramolecular coordination networks, with the metalated quinonoid or thioquinonoid linkers acting as backbones and the metal centers as nodes. This novel family of supramolecular assemblies exhibits short pi-pi and MM interactions. These results illustrate successfully the role of the organometallic linkers to produce an impressive range of novel supramolecular architectures that hold promise for the development of functional materials.

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Elemental Carbon Chain Bridging Two Iron Centers: Syntheses and Spectroscopic Properties of [Cp(dppe)Fe-C4-FeCp(dppe)]n+.cntdot.n[PF6]-. X-ray Crystal Structure of the Mixed Valence Complex (n = 1)

Cited by 435 publications

References 3 publications

Efficient Electronic Communication of Two Ruthenium Centers through a Rigid Ditopic N‐Heterocyclic Carbene Linker

Efficient Electronic Communication of Two Ruthenium Centers through a Rigid Ditopic N‐Heterocyclic Carbene Linker

Synthesis and electrochemical characterization of bimetallic ruthenium complexes with the bridging eta2(<FONT FACE=Symbol>s,s</FONT>)-1,3-butadiyne-1,4-diyl ligand

Supramolecular Assemblies Based on Organometallic Quinonoid Linkers: A New Class of Coordination Networks

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