Molecular Metal Clusters as Catalysts

Muetterties, E. L.

doi:10.1080/03602458108068069

Cited by 42 publications

(10 citation statements)

References 38 publications

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“…The preparations of all ligands with the exception of 3a have been described in an earlier paper. 3 2,6-Di(2'-[l,8]naphthyridyl)pyridine (3a). To a mixture of 0.33 g (2 mmol) of 2,6-diacetylpyridine and 0.49 g (4 mmol) of 2-aminonicotin-aldehyde23 in 20 mL of absolute ethanol was added a solution of 0.05 g of KOH in 2 mL of absolute ethanol.…”

Section: Methodsmentioning

confidence: 99%

“…Ru(3b)2[PF6]2. Treatment of 0.40 g of 3b with RuC13 for 36 h provided 0.35 g (75%) of the complex purified by method A: NMR ( 300MHz, CD3CN) 8.23 (dd, Hr, 7yr = 4.2 Hz, 7y r = 2.0 Hz), 8.15 (s, H4), 7.99 (dd, Hy, 7y,y = 8.1 Hz),'7.97 (s, H4,), 1.29 (dd, Hy), 3.65 (t, a-CH2, 7 = 7.8 Hz), 3.45 (t, a-CH2); LC-MS, m/e (relative intensity)…”

Section: Methodsmentioning

confidence: 99%

“…di [1,8]terpyridine (1) diquinolylpyridine (2) naphthyridylpyridine (3) h6, h4 species has the largest dihedral angle (117°) between the two quinoline rings yet almost the same N'-N" distance as the monomethylene derivative, where the quinoline rings are coplanar.…”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Polyaza cavity-shaped molecules. 9. Ruthenium(II) complexes of annelated derivatives of 2,2':6,2"-terpyridine and related systems: synthesis, properties, and structure

Thummel¹,

Jahng²

1986

Inorg. Chem.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Polyaza cavity-shaped molecules. 9. Ruthenium(II) complexes of annelated derivatives of 2,2':6,2"-terpyridine and related systems: synthesis, properties, and structure

Thummel¹,

Jahng²

1986

Inorg. Chem.

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“…Synthetic iron-carbide clusters are also known, though in these cases the carbides come from very different sources. − In a six-iron example, the Fe 6 cluster [Me 4 N] 2 [Fe 6 C(CO) 16 ] ( 19 , Figure a) was studied in the early 1970s as a model of possible intermediates in the iron-catalyzed Fischer–Tropsch process. , In collaboration with DeBeer, we recently reported more extensive crystallographic characterization of 19 , as well as X-ray emission studies that elucidated the electronic structure of the iron-carbide core and demonstrated the delocalized orbitals that give rise to Fe–C bonding . Oxidation of 19 leads to related Fe 5 and Fe 4 carbide/carbonyl clusters. , One transformation with particular relevance to the FeMoco mechanism is that [Fe 4 C(CO) 12 ] 2– ( 21 , Figure b) can be oxidized in the presence of H 2 to give neutral HFe 4 (CH)(CO) 12 ( 22 ). ,,, This product can also be synthesized through double protonation of the cluster. , The oxidative addition of H 2 is the microscopic reverse of reductive elimination from a hydride–iron cluster, and suggests that reversible formation of C–H bonds in the FeMoco should be considered as a possibility.…”

Section: Carbide Complexes and Iron–n2 Complexes With Carbon Ligandsmentioning

confidence: 99%

Insight into the Iron–Molybdenum Cofactor of Nitrogenase from Synthetic Iron Complexes with Sulfur, Carbon, and Hydride Ligands

2016

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Nitrogenase enzymes are used by microorganisms for converting atmospheric N2 to ammonia, which provides an essential source of N atoms for higher organisms. The active site of the molybdenum-dependent nitrogenase is the unique carbide-containing iron-sulfur cluster called the iron-molybdenum cofactor (FeMoco). On the FeMoco, N2 binding is suggested to occur at one or more iron atoms, but the structures of the catalytic intermediates are not clear. In order to establish the feasibility of different potential mechanistic steps during biological N2 reduction, chemists have prepared iron complexes that mimic various structural aspects of the iron sites in FeMoco. This reductionist approach gives mechanistic insight, and also uncovers fundamental principles that could be used more broadly for small molecule activation. Here, we review recent results and highlight directions for future research. In one direction, synthetic iron complexes have now been shown to bind N2, break the N-N triple bond, and produce ammonia catalytically. Carbon and sulfur based donors have been incorporated into the ligand spheres of Fe-N2 complexes to show how these atoms may influence the structure and reactivity of the FeMoco. Hydrides have been incorporated into synthetic systems, which can bind N2, reduce some nitrogenase substrates, and/or reductively eliminate H2 to generate reduced iron centers. Though some carbide-containing iron clusters are known, none yet have sulfide bridges or high-spin iron atoms like the FeMoco.

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“…Applications of cluster complexes in catalysis has stimulated great interest in the preparation and properties of heteronuclear clusters [1][2][3][4][5]. We are interested in cluster complexes containing a chiral tetrahedral skeleton because evidence for asymmetric induction by cluster-catalyzed reactions would provide definitively the proof that the clusters do not fragment during catalysis [4].…”

Section: Introductionmentioning

confidence: 99%

Studies of metal exchange reactions: the synthesis and structures of heteronuclear metal clusters containing the indenyl ligand (μ3-CR)Co2M(CO)8(η5- Ind)(R=H,CH3,C6H5,COOC2H5; M=Mo,W)

Zhang

Zhu

et al. 2004

Journal of Organometallic Chemistry

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Molecular Metal Clusters as Catalysts

Cited by 42 publications

References 38 publications

Polyaza cavity-shaped molecules. 9. Ruthenium(II) complexes of annelated derivatives of 2,2':6,2"-terpyridine and related systems: synthesis, properties, and structure

Polyaza cavity-shaped molecules. 9. Ruthenium(II) complexes of annelated derivatives of 2,2':6,2"-terpyridine and related systems: synthesis, properties, and structure

Insight into the Iron–Molybdenum Cofactor of Nitrogenase from Synthetic Iron Complexes with Sulfur, Carbon, and Hydride Ligands

Studies of metal exchange reactions: the synthesis and structures of heteronuclear metal clusters containing the indenyl ligand (μ3-CR)Co2M(CO)8(η5- Ind)(R=H,CH3,C6H5,COOC2H5; M=Mo,W)

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