Mono- and disubstituted derivatives of benzo[c]cinnolinebis(tricarbonyliron)

Ellgen, Paul C.; McMullin, Scott L.

doi:10.1021/ic50127a010

Cited by 19 publications

(2 citation statements)

References 1 publication

(1 reference statement)

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“…The units of the isotropic thermal parameters are A2. 6 For Fet the thermal parametersB22,B33,B12,B,3, andB23 are 49 (1), 34 (1),-12 (1), 20 (1), and -4 (1), respectively.…”

Section: Discussion Of the Carbonyl Substitution Mechanismmentioning

confidence: 99%

Mechanisms of substitution of ligand-bridged diiron hexacarbonyl complexes. .mu.-Butatriene-bis(tricarbonyliron) complexes: crystallographic determination of the structure of a carbonyl substitution product and evidence for a carbonyl-inserted intermediate

Gerlach¹,

Wing²,

Ellgen³

1976

Inorg. Chem.

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“…The units of the isotropic thermal parameters are A2. 6 For Fet the thermal parametersB22,B33,B12,B,3, andB23 are 49 (1), 34 (1),-12 (1), 20 (1), and -4 (1), respectively.…”

Section: Discussion Of the Carbonyl Substitution Mechanismmentioning

confidence: 99%

Mechanisms of substitution of ligand-bridged diiron hexacarbonyl complexes. .mu.-Butatriene-bis(tricarbonyliron) complexes: crystallographic determination of the structure of a carbonyl substitution product and evidence for a carbonyl-inserted intermediate

Gerlach¹,

Wing²,

Ellgen³

1976

Inorg. Chem.

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“…As for other donor ligands [26,28], PMe 3 displaced two of the CO ligands in 1 to afford the red-colored Fe 2 (BC)(CO) 4 (PMe 3 ) 2 (2) (Eq. (1)).…”

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confidence: 99%

Extending the motif of the [FeFe]-hydrogenase active site models: Protonation of Fe2(NR)2(CO)6−L species

Volkers

Rauchfuss

2007

Journal of Inorganic Biochemistry

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Studies on diiron dithiolato complexes have proven fruitful for modeling the active site of the [FeFe]hydrogenases. Here we present a departure from the classical Fe 2 S 2 motif by examining the viability of Fe 2 N 2 butterfly compounds as functional models for the diiron active site of [FeFe]-hydrogenases. Derivatization of Fe 2 (BC)(CO) 6 (1, BC = benzo-[c]-cinnoline) with PMe 3 affords Fe 2 (BC) (CO) 4 (PMe 3 ) 2 , which subsequently undergoes protonation at the Fe-Fe bond. The hydride [(μ-H) Fe 2 (BC)(CO) 4 (PMe 3 ) 2 ]PF 6 was characterized crystallographically as the C 2v isomer. It represents a rare example of a hydrido diiron complex that exists as observable isomers, depending on the location of the phosphine ligands -diapical and apical-basal. This hydride catalyzes the electrochemical reduction of protons. Keywords Fe complexes; Metal hydride; Hydrogenase; ElectrocatalysisIn recent years, many compounds of the type Fe 2 (S-R) 2 (CO) 4 L 2 have been prepared and examined as structural and functional models for the active site of [FeFe]-hydrogenases. Particular emphasis has been placed on variations of L, especially tertiary phosphines [1][2][3], but also isocyanides [4,5], N-heterocyclic carbenes [6][7][8][9], and cyanide [10][11][12][13]. While much effort has focused on functionalizing the dithiolate ligand [14][15][16][17][18][19][20], relatively little work has examined the possibility of replacing the thiolates with other bridging groups [21]. Best and coworkers demonstrated that the corresponding phosphides Fe 2 (PR 2 ) 2 (CO) 6 and [Fe 2 (PR 2 ) 2 (CO) 6 H] − are effective catalysts for hydrogen evolution [22].Incentives for broadening the range of bridging ligands include changing the steric profile of the catalysts, altering the susceptibility of the bridge toward electrophilic attack (important since these catalysts function in acidic media), incorporating functionality, and manipulating the electronic character (basicity, E 1/2 ) of the metals. Naturally, a fundamental motivation for investigating new bridging ligands is to elucidate the elementary design rules that will lead to greater mechanistic insight and, ultimately, a deeper understanding of hydrogenogenesis.Approximately 15 nitrogenous bridges are known to link pairs of iron centers, giving complexes of the general formula Fe 2 (NR 1,2 ) 2 (CO) 6 (Scheme 1). Many of the complexes were first reported in the 1960s and 1970s in an era where the interactions of nitrene-forming reagents and metal carbonyls were first systematized. We selected one representative of this series, Fe 2 (BC)(CO) 6 [23][24][25][26] properties would test most demandingly the scope of the hydrogenase behavior of the Fe 2 (μ-X) 2 L n systems (L = CO, donor ligands). This report summarizes these results, which indeed demonstrate the prospect that many nitrogenous bridging ligands could be applied to the modeling of hydrogenases.Compound 1 was prepared using the original method, using Fe 3 (CO) 12 in place of Fe(CO) 5 [27]. As for other donor ligands [26,...

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The Transition Metal Chemistry of Azo Compounds

Bruce

Goodall

The Chemistry of the Hydrazo, Azo and Azoxy Groups

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Mono- and disubstituted derivatives of benzo[c]cinnolinebis(tricarbonyliron)

Cited by 19 publications

References 1 publication

Mechanisms of substitution of ligand-bridged diiron hexacarbonyl complexes. .mu.-Butatriene-bis(tricarbonyliron) complexes: crystallographic determination of the structure of a carbonyl substitution product and evidence for a carbonyl-inserted intermediate

Mechanisms of substitution of ligand-bridged diiron hexacarbonyl complexes. .mu.-Butatriene-bis(tricarbonyliron) complexes: crystallographic determination of the structure of a carbonyl substitution product and evidence for a carbonyl-inserted intermediate

Extending the motif of the [FeFe]-hydrogenase active site models: Protonation of Fe2(NR)2(CO)6−L species

The Transition Metal Chemistry of Azo Compounds

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