Iron- and Ruthenium-Containing Triple-Decker Complexes with a Central Pentaphospholyl Ligand − X-ray Structures of [(η-C5H5)Fe(μ-η:η-P5)Ru(η-C5Me5)]PF6 and [(η-C5Me5)Ru(μ-η:η-P5)Ru(η-C5Me5)]PF6

Kudinov, Alexander R.; Loginov, Dmitry A.; Starikova, Z. A.; Petrovskii, P. V.; Corsini, Maddalena; Zanello, Piero

doi:10.1002/1099-0682(200211)2002:11<3018::aid-ejic3018>3.0.co;2-a

Cited by 73 publications

(18 citation statements)

References 23 publications

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“…In addition, the C–C bonds within the bridging Cp′ ring (average 1.462 Å) are significantly longer than those in free Cp′ 2 Fe (1.422 Å) but close to those in Cp* 2 Fe (1.461 Å). To the extent that bond length can be correlated with bond strength, these data suggest weaker Fe–C and C–C interactions for the bifacially coordinated bridging ring in comparison with the singly coordinated terminal rings. , …”

Section: Resultsmentioning

confidence: 94%

“…27 To the extent that bond length can be correlated with bond strength, these data suggest weaker Fe−C and C−C interactions for the bifacially coordinated bridging ring in comparison with the singly coordinated terminal rings. 30,31 Mossbauer effect (ME) spectroscopy of 1•BF 4 accumulated over the temperature interval 90 < T < 273 K evidenced the expected doublet spectra for diamagnetic Fe(II), and a typical spectrum is shown in Figure 2.…”

Section: ■ Introductionmentioning

confidence: 94%

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Syntheses, Structures, and Mössbauer Effect Spectroscopy of Triple-Decker Complexes Incorporating Nonamethylferrocene

et al. 2015

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Three new triple-decker complexes were synthesized by the reaction of nonamethylferrocene, Cp′FeCp* (Cp′ = C5Me4H, Cp* = C5Me5), with coordinatively unsaturated transition-metal complexes. The reaction of ruthenium cations [(C5R5)Ru]+ (R = H, Me) with Cp′FeCp* afforded the purple heterometallic triple-decker complexes [(C5R5)Ru(μ-Cp′)FeCp*]+ by electrophilic addition of ruthenium to the Cp′ ring of nonamethylferrocene. The analogous reaction with the manganese cation [Mn(CO)3]+ produced the blue homometallic triple-decker complex [Cp*Fe(μ-Cp′)FeCp*]+ by abstraction of the Cp′ ring from Cp′FeCp* and subsequent addition of the newly generated cation [Cp*Fe]+ to 1 equiv of Cp′FeCp*. These experiments demonstrate that the asymmetry of Cp′FeCp* gives rise to a remarkable degree of regioselectivity such that ruthenium electrophiles add only to the Cp′ ring and never to the Cp* ring. In a similar way, [Mn(CO)3]+ abstracts only the Cp′ ring from Cp′FeCp* to produce [Cp*Fe]+, which in turn adds only to the Cp′ ring of Cp′FeCp* to produce [Cp*Fe(μ-Cp′)FeCp*]+. Three air-stable triple-decker complexes incorporating nonamethylferrocene, [Cp*Fe(μ-Cp′)FeCp*]+ (1), [CpRu(μ-Cp′)FeCp*]+ (2), and [Cp*Ru(μ-Cp′)FeCp*]+ (3), have been characterized by NMR spectroscopy, elemental analysis, single-crystal X-ray diffraction analysis, and temperature-dependent 57Fe Mössbauer spectroscopy.

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Section: Resultsmentioning

confidence: 94%

Section: ■ Introductionmentioning

confidence: 94%

Syntheses, Structures, and Mössbauer Effect Spectroscopy of Triple-Decker Complexes Incorporating Nonamethylferrocene

et al. 2015

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“…These structural differences between the inner and outer ligands in complexes 1 – 5 may be attributed to the fact that bifacial coordination to ruthenium(II) atoms reduces electron density in the bridging ring compared with the singly coordinated terminal rings. Moreover, insofar as bond length can be correlated with bond strength, these data suggest weaker Ru–C and C–C interactions for the doubly coordinated central ring compared with the singly coordinated outer rings …”

Section: Results and Discussionmentioning

confidence: 99%

Syntheses and Structures of Triple-Decker Complexes Incorporating Octamethylruthenocene and Nonamethylruthenocene

et al. 2019

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Five new diruthenium triple-decker complexes were synthesized by the reaction of ruthenium electrophiles with metallocenes of ruthenium. At 40 °C, the reaction of [(C5R5)Ru(NCMe)3]+ (R = H, Me) with octamethylruthenocene, Cp′RuCp′ (Cp′ = C5Me4H), afforded orange diruthenium triple-decker complexes [(C5R5)Ru(μ-Cp′)RuCp′]+ by electrophilic addition of [(C5R5)Ru]+ to a Cp′ ring of octamethylruthenocene. However, at 100 °C, [(C5H5)Ru]+ abstracted a Cp′ ring from Cp′RuCp′ generating [Cp′Ru]+ and CpRuCp′ (Cp = C5H5) by a ligand transfer reaction. Subsequent addition of the newly generated cation [Cp′Ru]+ to an equivalent of Cp′RuCp′ afforded a triple-decker complex with three tetramethylcyclopentadienyl rings, [Cp′Ru(μ-Cp′)RuCp′]+. Analogous reactions between [(C5R5)Ru(NCMe)3]+ and nonamethylruthenocene, Cp′RuCp* (Cp* = C5Me5), afforded orange triple-decker complexes [(C5R5)Ru(μ-Cp′)RuCp*]+ by direct electrophilic addition. These reactions with the asymmetric metallocene, Cp′RuCp*, demonstrate a remarkable degree of regioselectivity such that electrophiles add only to the Cp′ ring and never to the Cp* ring of nonamethylruthenocene. The five diruthenium triple-decker complexes have been fully characterized by NMR spectroscopy, elemental analyses, and single crystal X-ray diffraction analyses, and nonamethylruthenocene, Cp*RuCp′, has been characterized by NMR and elemental analysis.

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“…In particular, polycyclic arenes, [16,17] cyclophanes, [18] dendrimers, [19] and polymers [20] have been synthesized this way. On the other hand, the same photochemical reaction has been used in organometallic chemistry for the synthesis of (C 5 R 5 )Fe(L) x complexes with various ligands [21–24] . In the absence of appropriate ligands, the initially formed [(C 5 R 5 )Fe] + species undergo further decomposition to give Fe 2+ ions, which can be used for photocatalytic polymerization of epoxides [25,26] and cyanates, [27] as well as for photoprinting by coordination with salicylate organic dyes [28,29] (interestingly some ferrocene derivatives can be also used in a similar way) [30,31] .…”

Section: Introductionmentioning

confidence: 99%

Generation of Cyclopentadiene for Diels–Alder Reactions by Visible‐Light Irradiation of Iron Sandwich Complexes

Sokolov

Polezhaev

Nelyubina

et al. 2022

Helvetica Chimica Acta

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Cyclopentadienes readily undergo fast and selective Diels-Alder reactions which can be used for conjugation of biomolecules and polymers. Herein we present a new method for the photochemical generation of cyclopentadienes by the visible light irradiation of the iron complexes [(C 5 H 4 R)Fe(arene)] + . This reaction proceeds at room temperature, in water, and in the presence of potentially interfering amino acids. Free cyclopentadiene is trapped by dienophiles to give the corresponding Diels-Alder adducts in 72-95 % yield.

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Iron- and Ruthenium-Containing Triple-Decker Complexes with a Central Pentaphospholyl Ligand − X-ray Structures of [(η-C5H5)Fe(μ-η:η-P5)Ru(η-C5Me5)]PF6 and [(η-C5Me5)Ru(μ-η:η-P5)Ru(η-C5Me5)]PF6

Cited by 73 publications

References 23 publications

Syntheses, Structures, and Mössbauer Effect Spectroscopy of Triple-Decker Complexes Incorporating Nonamethylferrocene

Syntheses, Structures, and Mössbauer Effect Spectroscopy of Triple-Decker Complexes Incorporating Nonamethylferrocene

Syntheses and Structures of Triple-Decker Complexes Incorporating Octamethylruthenocene and Nonamethylruthenocene

Generation of Cyclopentadiene for Diels–Alder Reactions by Visible‐Light Irradiation of Iron Sandwich Complexes

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