Binuclear hexafluorocyclopentadiene iron carbonyls: bis(dihapto) versus trihapto–monohapto bonding in iron–iron bonded structures

Deng, Jianming; Li, Qianshu; Xie, Yaoming; King, R. B.; Schaefer, Henry F.

doi:10.1039/c3nj00311f

Cited by 6 publications

(5 citation statements)

References 37 publications

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“…The WBIs (0.63–0.68) of the SiFe bonds in 3‐Me are similar to that for 2‐Me (0.69). The 0.36 WBI of the FeFe bond in 3‐Me (Figure S2b)17 is consistent with those (0.34–0.35) of the iron–iron single bonds in the singlet binuclear iron carbonyl complexes [i.e., (C 5 F 6 )Fe 2 (CO) 7 ] 27…”

Section: Methodssupporting

confidence: 73%

Transition‐Metal‐Mediated Cleavage of a SiSi Double Bond

et al. 2015

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Reaction of carbene‐stabilized disilicon (1) with Fe(CO)5 gives the 1:1 adduct L:SiSi[Fe(CO)4]:L (L:=C{N(2,6‐Pri2C6H3)CH}2) (2) at room temperature. At raised temperature, however, 2 may react with another equivalent of Fe(CO)5 to give L:Si[μ‐Fe2(CO)6](μ‐CO)Si:L (3) through insertion of both CO and Fe2(CO)6 into the Si2 core, which represents the first experimental realization of transition metal‐carbonyl‐mediated cleavage of a SiSi double bond. The structures and bonding of both 2 and 3 have been investigated by spectroscopic, crystallographic, and computational methods.

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Section: Methodssupporting

confidence: 73%

Transition‐Metal‐Mediated Cleavage of a SiSi Double Bond

et al. 2015

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“…Table also gives BP86 results for the hexafluorocyclopentadiene diiron carbonyl series (C 5 F 6 )Fe 2 (CO) n ( n = 8, 7, 6, and 5) among which the octacarbonyl (C 5 F 6 )Fe 2 (CO) 8 is known experimentally (Banks and Haszeldine). These complexes have a neutral Fe 2 core.…”

Section: Iron–iron Bondsmentioning

confidence: 99%

“…The cyclopentadienyl (C 5 H 5 ) 2 Fe 2 (CO) n series (Table ) exhibits the following length ranges for iron–iron bonds: 2.63 ± 0.09 Å for Fe–Fe single bonds, 2.264 Å for the sole example of an FeFe double bond, 2.16 ± 0.05 Å for FeFe triple bonds, and 2.069 Å for the sole example of an Fe–Fe quadruple bond. The hexafluorocyclopentadiene (C 5 F 6 ) 2 Fe 2 (CO) n series (Table ) exhibits the following length ranges for iron–iron bonds: 2.802 Å for the sole example of an Fe–Fe single bond, 2.45 ± 0.11 Å for FeFe double bonds, and 2.278 Å for the sole example of an FeFe triple bond. The pentalene (C 8 H 6 )Fe 2 (CO) n series (Table ) exhibits the following length ranges for iron–iron bonds: 2.69 ± 0.06 Å for Fe–Fe single bonds, 2.47 ± 0.17 Å for FeFe double bonds, and 2.304 Å for the sole example of an FeFe triple bond.…”

Section: Iron–iron Bondsmentioning

confidence: 99%

Metal–Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc

2018

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This survey of metal–metal (MM) bond distances in binuclear complexes of the first row 3d-block elements reviews experimental and computational research on a wide range of such systems. The metals surveyed are titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, and zinc, representing the only comprehensive presentation of such results to date. Factors impacting MM bond lengths that are discussed here include (a) the formal MM bond order, (b) size of the metal ion present in the bimetallic core (M2) n+, (c) the metal oxidation state, (d) effects of ligand basicity, coordination mode and number, and (e) steric effects of bulky ligands. Correlations between experimental and computational findings are examined wherever possible, often yielding good agreement for MM bond lengths. The formal bond order provides a key basis for assessing experimental and computationally derived MM bond lengths. The effects of change in the metal upon MM bond length ranges in binuclear complexes suggest trends for single, double, triple, and quadruple MM bonds which are related to the available information on metal atomic radii. It emerges that while specific factors for a limited range of complexes are found to have their expected impact in many cases, the assessment of the net effect of these factors is challenging. The combination of experimental and computational results leads us to propose for the first time the ranges and “best” estimates for MM bond distances of all types (Ti–Ti through Zn–Zn, single through quintuple).

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“…TheW BIs (0.63-0.68) of the SiÀFe bonds in 3-Me are similar to that for 2-Me (0.69). [27] Compound 3 was prepared by reaction of 1 with Fe(CO) 5 through isolable intermediate 2.Incontrast to 4,compound 2 does not exhibit dynamic complexation behavior, which may be due to the strong steric repulsion between the carbene ligands and Fe(CO) 4 fragment. [27] Compound 3 was prepared by reaction of 1 with Fe(CO) 5 through isolable intermediate 2.Incontrast to 4,compound 2 does not exhibit dynamic complexation behavior, which may be due to the strong steric repulsion between the carbene ligands and Fe(CO) 4 fragment.…”

Section: Methodsmentioning

confidence: 61%

“…The0 .36 WBI of the FeÀFe bond in 3-Me ( Figure S2b) [17] is consistent with those (0.34-0.35) of the iron-iron single bonds in the singlet binuclear iron carbonyl complexes [i.e., (C 5 F 6 )Fe 2 (CO) 7 ]. [27] Compound 3 was prepared by reaction of 1 with Fe(CO) 5 through isolable intermediate 2.Incontrast to 4,compound 2 does not exhibit dynamic complexation behavior, which may be due to the strong steric repulsion between the carbene ligands and Fe(CO) 4 fragment. Thet ransformation of 2 to 3 involves the insertions of both CO and Fe 2 (CO) 6 into the two LDSi units,which represents the first realization of transitionmetal-carbonyl-mediated cleavage of aS i = Si double bond.…”

mentioning

confidence: 99%

Transition‐Metal‐Mediated Cleavage of a SiSi Double Bond

et al. 2015

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Reaction of carbene-stabilized disilicon (1) with Fe(CO)5 gives the 1:1 adduct L:Si=Si[Fe(CO)4 ]:L (L:=C{N(2,6-Pr(i) 2 C6 H3 )CH}2 ) (2) at room temperature. At raised temperature, however, 2 may react with another equivalent of Fe(CO)5 to give L:Si[μ-Fe2 (CO)6 ](μ-CO)Si:L (3) through insertion of both CO and Fe2 (CO)6 into the Si2 core, which represents the first experimental realization of transition metal-carbonyl-mediated cleavage of a Si=Si double bond. The structures and bonding of both 2 and 3 have been investigated by spectroscopic, crystallographic, and computational methods.

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Binuclear hexafluorocyclopentadiene iron carbonyls: bis(dihapto) versus trihapto–monohapto bonding in iron–iron bonded structures

Cited by 6 publications

References 37 publications

Transition‐Metal‐Mediated Cleavage of a SiSi Double Bond

Transition‐Metal‐Mediated Cleavage of a SiSi Double Bond

Metal–Metal (MM) Bond Distances and Bond Orders in Binuclear Metal Complexes of the First Row Transition Metals Titanium Through Zinc

Transition‐Metal‐Mediated Cleavage of a SiSi Double Bond

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