Metal–ligand bonding and metal atom dynamics in Fe–Fe and Ru–Fe triple-decker sandwich complexes

Fagnan, Erin N.; Watson, Eric J.; Nowik, I.; Herber, Rolfe H.

doi:10.1016/j.jorganchem.2014.05.012

Cited by 6 publications

(6 citation statements)

References 21 publications

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“…The ME parameters (isomer shift IS and quadrupole splitting QS) at 90 K, as well as the derived parameters, are summarized in Table . The IS at 90 K (0.550(2) mm s –1 ), which is related to the electron density at the ME resonant atom, is very similar to that reported earlier for [Cp′FeCp′FeCp′]BF 4 (0.520(6) mm s –1 ) . For comparison purposes, the ME parameters for free ferrocene at 90 K are IS = 0.537(10) mm s –1 and QS = 2.418(1) mm s –1 .…”

Section: Resultssupporting

confidence: 83%

“…At the present time, the reason for this disagreement is not well understood. However, it is noteworthy that the calculated value for k 2 ⟨ x 2 ⟩ for [CpRu(μ-Cp′)FeCp*]PF 6 is very similar to that for [CpRu(μ-Cp′)FeCp′]PF 6 reported earlier . As was the case for compound 1· BF 4 , the temperature dependence of the area ratio over the range 97 < T < 243 K is negligibly small ( A = 1.01 ± 1), again indicating isotropic motion of the Fe atom in this compound.…”

Section: Resultssupporting

confidence: 77%

“…The IS at 90 K (0.550(2) mm s –1 ), which is related to the electron density at the ME resonant atom, is very similar to that reported earlier for [Cp′FeCp′FeCp′]BF 4 (0.520(6) mm s –1 ) . For comparison purposes, the ME parameters for free ferrocene at 90 K are IS = 0.537(10) mm s –1 and QS = 2.418(1) mm s –1 . The temperature dependence of the IS is well fitted by a linear regression ( R = 0.99 for 16 data points) and leads to the calculated effective vibrational mass M eff = 92(2) daltons (Da).…”

Section: Resultsmentioning

confidence: 99%

“…32 For comparison purposes, the ME parameters for free ferrocene at 90 K are IS = 0.537(10) mm s −1 and QS = 2.418(1) mm s −1 . 32 The temperature dependence of the IS is well fitted by a linear regression (R = 0.99 for 16 data points) and leads to the calculated effective vibrational mass M eff = 92(2) daltons (Da). The difference between this value and the bare iron atom mass of 57 Da is, of course, due to the covalency of the Fe−C ligation.…”

Section: ■ Introductionmentioning

confidence: 99%

“…At the present time, the reason for this disagreement is not well understood. However, it is noteworthy that the calculated value for k 2 ⟨x 2 ⟩ for [CpRu(μ-Cp′)FeCp*]PF 6 is very similar to that for [CpRu(μ-Cp′)FeCp′]PF 6 reported earlier 32. As was the case for compound 1•BF 4 , the temperature dependence of the…”

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confidence: 99%

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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: Resultssupporting

confidence: 83%

Section: Resultssupporting

confidence: 77%

Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

“…At the present time, the reason for this disagreement is not well understood. However, it is noteworthy that the calculated value for k 2 ⟨x 2 ⟩ for [CpRu(μ-Cp′)FeCp*]PF 6 is very similar to that for [CpRu(μ-Cp′)FeCp′]PF 6 reported earlier 32. As was the case for compound 1•BF 4 , the temperature dependence of the…”

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confidence: 99%

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