Stereochemical Control of Iron(II) Complexes Containing a Diphosphine Ligand with a Pendant Nitrogen Base

Henry, R. M.; Shoemaker, Richard K.; Newell, Rachel; Jacobsen, George M.; DuBois, Daniel L.; DuBois, M. Rakowski

doi:10.1021/om050071c

Cited by 67 publications

(69 citation statements)

References 46 publications

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“…The R , R ‐substituted cyclohexyl group causes an asymmetry in the placement of the two phenyl groups next to each acetonitrile binding site. The FeP bond lengths are between those observed for the low‐spin iron(II) complex cis ‐[Fe(CO)(NCMe)(PEt 2 CH 2 NMeCH 2 PEt 2 )(PMe 2 CH 2 PMe 2 )](BF 4 ) 2 (FeP 2.30–2.38 Å)19 and those observed in the complexes trans ‐[FeH(NCMe)(PEt 2 CH 2 NMeCH 2 PEt 2 )(PMe 2 CH 2 PMe 2 )](BF 4 ) (FeP 2.20–2.22 Å)19 and trans ‐[Fe(H 2 )H(dppe) 2 ](BPh 4 ) (FeP 2.23–2.25 Å)20 while the FeN3 and FeN4 bond lengths are similar to that of the former (carbonyl) complex.…”

Section: Methodsmentioning

confidence: 59%

Highly Efficient Catalyst Systems Using Iron Complexes with a Tetradentate PNNP Ligand for the Asymmetric Hydrogenation of Polar Bonds

et al. 2008

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Iron competes with pricey ruthenium: The first catalyst systems using iron complexes for asymmetric H2 hydrogenation at 50 °C and asymmetric transfer hydrogenation at room temperature has been discovered. The transfer hydrogenation activity is similar to that of the best ruthenium catalyst. Surprisingly, the precatalysts have a tetradentate diiminodiphosphine ligand which has no NH functionality.

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Section: Methodsmentioning

confidence: 59%

Highly Efficient Catalyst Systems Using Iron Complexes with a Tetradentate PNNP Ligand for the Asymmetric Hydrogenation of Polar Bonds

et al. 2008

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“…[6,9] The Fe-C distance is 1.775(4) and the Fe-C-O angle is 174.89(6)8, both of which are typical for Fe II carbonyl compounds. [10] All of the other bond distances and angles are very similar to those in the starting material,…”

Section: Introductionmentioning

confidence: 52%

“…Characteristic IR absorptions for n CO were found for both compounds: at 2002 cm À1 in 1 and 2004 cm À1 in 3. These are typical values for dicationic iron(II)-coordinated carbonyl ligands: [10] n CO in (R,R)-2, for example, is 2000 cm À1 , whereas n CO in the Fe II complex cis-[Fe(CO)-…”

Section: Introductionmentioning

confidence: 90%

Iron(II) Complexes for the Efficient Catalytic Asymmetric Transfer Hydrogenation of Ketones

Meyer

Lough

Morris

2009

Chemistry A European J

174

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Iron(II) carbonyl compounds of the type trans-[Fe(NCMe)(CO)(P-N-N-P)][BF(4)](2) bearing the ethylenediamine-derived diiminodiphosphine ligands (R,R)- or (S,S)-1,2-diphenyl-1,2-diaminoethane were synthesized and characterized, including by their crystal structures. The new complexes are suitable precatalysts for the transfer hydrogenation of ketones at room temperature, giving turnover frequencies of up to 2600 h(-1) with low catalyst loadings (0.025-0.17%). Screening experiments showed that the precatalysts are able to produce alcohols from a wide range of simple ketones. For sterically demanding prochiral ketones, excellent enantioselectivities were obtained (up to 96% ee).

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“…6 or other Lewis-basic site (127). Such heterolysis has recently been shown to occur on a mononuclear Fe complex with a pendant nitrogen base (132). Nature apparently designed these enzymes billions of years ago to use the CO ligand, whose strong trans influence (135,136).…”

Section: Reactivity Of -Complexes: Acidity and Heterolysis Of X-h Bondsmentioning

confidence: 99%

Dihydrogen complexes as prototypes for the coordination chemistry of saturated molecules

Kubas

2007

Proc. Natl. Acad. Sci. U.S.A.

179

105

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The binding of a dihydrogen molecule (H2) to a transition metal center in an organometallic complex was a major discovery because it changed the way chemists think about the reactivity of molecules with chemically ''inert'' strong bonds such as H-H and C-H. Before the seminal finding of side-on bonded H2 in W(CO)3(PR3)2(H2), it was generally believed that H2 could not bind to another atom in stable fashion and would split into two separate H atoms to form a metal dihydride before undergoing chemical reaction. Metalbound saturated molecules such as H2, silanes, and alkanes (-complexes) have a chemistry of their own, with surprisingly varied structures, bonding, and dynamics. H2 complexes are of increased relevance for H2 production and storage in the hydrogen economy of the future.

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Stereochemical Control of Iron(II) Complexes Containing a Diphosphine Ligand with a Pendant Nitrogen Base

Cited by 67 publications

References 46 publications

Highly Efficient Catalyst Systems Using Iron Complexes with a Tetradentate PNNP Ligand for the Asymmetric Hydrogenation of Polar Bonds

Highly Efficient Catalyst Systems Using Iron Complexes with a Tetradentate PNNP Ligand for the Asymmetric Hydrogenation of Polar Bonds

Iron(II) Complexes for the Efficient Catalytic Asymmetric Transfer Hydrogenation of Ketones

Dihydrogen complexes as prototypes for the coordination chemistry of saturated molecules

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