Transition metals in organic synthesis: Highlights for the year 2005

Söderberg, Björn C.G.

doi:10.1016/j.ccr.2007.03.011

Cited by 24 publications

(6 citation statements)

References 1,545 publications

(1,701 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In support of this hypothesis, dithiolation is obtained in the absence of H 2 O (26) [183]. In the presence of CO, thiocarbonylation occurs (27) [183]. Further advances are expected to improve the selectivity of this process.…”

Section: Equation 25supporting

confidence: 52%

Organometallic Approaches to Carbon–Sulfur Bond Formation

2010

View full text Add to dashboard Cite

show abstract

Section: Equation 25supporting

confidence: 52%

Organometallic Approaches to Carbon–Sulfur Bond Formation

2010

View full text Add to dashboard Cite

show abstract

“…Transition metal organometallic reactions have become increasingly important in the synthesis of organic molecules . Underscoring this crucial role are three Nobel Prizes in the past dozen years awarded for palladium-catalyzed cross-coupling in 2010, olefin metathesis in 2005, and asymmetric catalysis in 2001 .…”

Section: Introductionmentioning

confidence: 99%

Modules for Introducing Organometallic Reactions: A Bridge between Organic and Inorganic Chemistry

2015

View full text Add to dashboard Cite

Transition metal organometallic reactions have become increasingly important in the synthesis of organic molecules. A new approach has been developed to introduce organometallic chemistry, along with organic and inorganic chemistry, at the foundational level. This change highlights applications of organometallic chemistry that have dramatically evolved in recent decades. With this development, a larger number of students have been reached than would typically be exposed to organometallic reactions. Modules are described that introduce transition metal organometallic compounds and reactions by analogy with thematically similar topics in general chemistry and organic chemistry. These topics are periodically reinforced by incorporation into organic synthesis problems.

show abstract

“…Recently, Kaye and Long have succeeded in grafting Cr(CO) 3 species on benzene rings of MOF-5 . The (η 6 -arene)Cr(CO) 3 's are interesting compounds for essentially two reasons: first, they serve as building blocks in organometallic chemistry and play important roles in heterogeneous catalysis. − Moreover, M(CO) n coordination entities (M = Cr, Mo and W, n ≤ 6) undergo UV light-activated substitution of a CO ligand by N 2 or H 2 , as demonstrated in solution studies, matrix isolation experiments, and supercritical fluids . This ability is maintained if the (η 6 -arene)Cr(CO) 3 is isolated in a polyethylene matrix or the Cr(CO) 3 species are grafted on the structural MOFs' benzene rings, with potential applications in the hydrogen storage field.…”

Section: Introductionmentioning

confidence: 99%

Stability and Reactivity of Grafted Cr(CO)₃Species on MOF Linkers: A Computational Study

Vitillo¹,

Groppo²,

Bordiga³

et al. 2009

Inorg. Chem.

View full text Add to dashboard Cite

The possibility to modulate Cr(CO)(3) properties by grafting it onto metal-organic framework (MOF) linkers of different natures has been investigated using density functional methods. MOF linkers were modeled using clusters constituted by benzene rings doubly substituted in the para position. The effect of the electron-donor or electron-acceptor nature of benzene substituents on the stability of the (eta(6)-arene)Cr(CO)(3) adduct and on the shift of the CO bands has been considered. Different electron-donor (-NH(2), -CH(3), -OH, -COONa) and electron-acceptor (-F, -COOH, -CN, -CF(3)) substituents have been used and the results compared with the bare benzene. C(6)H(4)(COOZnOH)(2) and C(6)H(4)(Zn(4)O(13)C(6)H(5))(2) clusters have also been adopted as models of the MOF-5 benzene rings. The possibility of modulating the stability and the reactivity of Cr(CO)(3) species by grafting them to MOFs with different organic linkers was verified. In particular, this study indicates that electron-acceptor (e.g., C(6)H(4)(COOH)(2)) substituted MOF linkers facilitate the substitution of CO by incoming molecules, whereas the use of electron-donor ones (e.g., C(6)H(4)(OH)(2)) would improve the stability of the Cr(CO)(3) adduct and the ring acidity. Furthermore, an almost linear dependence of the Cr(CO)(3) binding energies on the calculated structural and vibrational features of the tricarbonyl was found, suggesting that the stability of the Cr(CO)(3) adduct can be inferred experimentally from vibrational and diffraction data. In the end, on the basis of the results obtained, it was possible to successfully explain the experimental shift of the CO IR stretching features of grafted Cr(CO)(3) on the UiO-66, CPO-27-Ni, and MOF-5 aromatic linkers and on the benzene rings of poly(ethylstyrene-co-divinylbenzene). The sign of the Delta nu(CO) shift with respect to C(6)H(6)Cr(CO)(3) has been found to be strongly dependent on higher/lower electron density on the ring.

show abstract

Transition metals in organic synthesis: Highlights for the year 2005

Cited by 24 publications

References 1,545 publications

Organometallic Approaches to Carbon–Sulfur Bond Formation

Organometallic Approaches to Carbon–Sulfur Bond Formation

Modules for Introducing Organometallic Reactions: A Bridge between Organic and Inorganic Chemistry

Stability and Reactivity of Grafted Cr(CO)₃Species on MOF Linkers: A Computational Study

Contact Info

Product

Resources

About

Transition metals in organic synthesis: Highlights for the year 2005

Cited by 24 publications

References 1,545 publications

Organometallic Approaches to Carbon–Sulfur Bond Formation

Organometallic Approaches to Carbon–Sulfur Bond Formation

Modules for Introducing Organometallic Reactions: A Bridge between Organic and Inorganic Chemistry

Stability and Reactivity of Grafted Cr(CO)3Species on MOF Linkers: A Computational Study

Contact Info

Product

Resources

About

Stability and Reactivity of Grafted Cr(CO)₃Species on MOF Linkers: A Computational Study