The reactions of pyridinyl thioesters with triiron dodecacarbonyl: their novel diiron carbonyl complexes and mechanistic investigations

2012 ◽  
Vol 41 (31) ◽  
pp. 9482 ◽  
Author(s):  
Li Long ◽  
Zhiyin Xiao ◽  
Giuseppe Zampella ◽  
Zhenhong Wei ◽  
Luca De Gioia ◽  
...  
Keyword(s):  
Carbonyl Complexes ◽  
Triiron Dodecacarbonyl ◽  
Mechanistic Investigations

MULTIPLE SCATTERING EFFECTS IN THE COBALT K-EDGE EXAFS OF METAL CARBONYL COMPLEXES

1986 ◽  
Vol 47 (C8) ◽  
pp. C8-589-C8-592
Author(s):  
N. BINSTED ◽  
S. L. COOK ◽  
J. EVANS ◽  
R. J. PRICE ◽  
G. N. GREAVES
Keyword(s):  
Multiple Scattering ◽  
Metal Carbonyl ◽  
Carbonyl Complexes ◽  
Metal Carbonyl Complexes ◽  
Scattering Effects ◽  
Multiple Scattering Effects

Three-Component [1+1+1] Cyclopropanation with Ruthenium(II)

2018 ◽  
Author(s):  
Tanner C. Jankins ◽  
Robert R. Fayzullin ◽  
Eugene Khaskin
Keyword(s):  
Quaternary Carbon ◽  
Poor Control ◽  
One Step ◽  
Synthetic Routes ◽  
Mechanistic Investigations ◽  
Chiral Centers ◽  
Metal Catalyzed ◽  
The Right ◽  
Substituted Cyclopropanes

We report a one-step, Ru(II)-catalyzed cyclopropanation reaction that is conceptually different from the previously reported protocols that include Corey-Chaykovsky, Simmons-Smith, and metal catalyzed carbene attack on olefins. Under the current protocol, various alcohols are transformed into sulfone substituted cyclopropanes with excellent isolated yields and diastereoselectivities. This new reaction forms highly congested cyclopropane products with three new C–C bonds, three or two new chiral centers and one new quaternary carbon center. 22 examples of isolated substrates are given. Previously reported synthetic routes for similar substrates are all multi-step, linear routes that proceed with overall low yields and poor control of stereochemistry. Experimental mechanistic investigations suggest initial metal-catalyzed dehydrogenation of the alcohol substrate and catalyst independent stepwise attack of two equivalents of sulfone on the aldehyde under basic conditions. While the Ru(II) is only responsible for the initial dehydrogenation step, the rate of aldehyde formation is crucial to maintaining the right balance of intermediates needed to afford the cyclopropane product.

Visible Light-Induced Sulfonylation/Arylation of Styrenes in a Double Radical Three-Component Photoredox Reaction

2019 ◽  
Author(s):  
Benjamin Lipp ◽  
Lisa Marie Kammer ◽  
Murat Kucukdisli ◽  
Adriana Luque ◽  
Jonas Kühlborn ◽  
...  
Keyword(s):  
Visible Light ◽  
Radical Formation ◽  
Three Component Reaction ◽  
Broad Variety ◽  
Styrene Derivatives ◽  
Mechanistic Investigations

Simultaneous sulfonylation/arylation of styrene derivatives is achieved in a photoredox-catalyzed three-component reaction using visible light. A broad variety of difunctionalized products is accessible in mostly excellent yields and high diastereoselectivity. The developed reaction is scalable and suitable for the modification of styrene-functionalized biomolecules. Mechanistic investigations suggest the transformation to be operating through a designed sequence of radical formation and radical combination.<br>

Redox Potential - (Electronic) Structure Relationships in 18- and 17-Electron Mononitrile (or Monocarbonyl) Diphosphine Complexes of Re and Fe

2001 ◽  
Vol 66 (1) ◽  
pp. 139-154 ◽  
Author(s):  
M. Fátima C. Guedes Da Silva ◽  
Luísa M. D. R. S. Martins ◽  
João J. R. Fraústo Da Silva ◽  
Armando J. L. Pombeiro
Keyword(s):  
Cyclic Voltammetry ◽  
Electronic Structure ◽  
Binding Sites ◽  
Closed Shell ◽  
Carbonyl Complexes ◽  
Metal Centre ◽  
Pt Electrode ◽  
Metal Site ◽  
Oxidation Potentials ◽  
First Time

The organonitrile or carbonyl complexes cis-[ReCl(RCN)(dppe)2] (1) (R = 4-Et2NC6H4 (1a), 4-MeOC6H4 (1b), 4-MeC6H4 (1c), C6H5 (1d), 4-FC6H4 (1e), 4-ClC6H4 (1f), 4-O2NC6H4 (1g), 4-ClC6H4CH2 (1h), t-Bu (1i); dppe = Ph2PCH2CH2PPh2), or cis-[ReCl(CO)(dppe)2] (2), as well as trans-[FeBr(RCN)(depe)2]BF4 (3) (R = 4-MeOC6H4 (3a), 4-MeC6H4 (3b), C6H5 (3c), 4-FC6H4 (3d), 4-O2NC6H4 (3e), Me (3f), Et (3g), 4-MeOC6H4CH2 (3h); depe = Et2PCH2CH2PEt2), novel trans-[FeBr(CO)(depe)2]BF4 (4) and trans-[FeBr2(depe)2] (5) undergo, as revealed by cyclic voltammetry at a Pt-electrode and in aprotic non-aqueous medium, two consecutive reversible or partly reversible one-electron oxidations assigned as ReI → ReII → ReIII or FeII → FeIII → FeIV. The corresponding values of the oxidation potentials IE1/2ox and IIE1/2ox (waves I and II, respectively) correlate with the Pickett's and Lever's electrochemical ligand and metal site parameters. This allows to estimate these parameters for the various nitrile ligands, depe and binding sites (for the first time for a FeIII/IV couple). The electrochemical ligand parameter show dependence on the "electron-richness" of the metal centre. The values of IE1/2ox for the ReI complexes provide some supporting for a curved overall relationship with the sum of Lever's electrochemical ligand parameter. The Pickett parametrization for closed-shell complexes is extended now also to 17-electron complexes, i.e. with the 15-electron ReII and FeIII centres in cis-{[ReCl(dppe)2]}+ and trans-{FeBr(depe)2}2+, respectively.

Transition Metal Carbonyl Complexes of an N-Heterocyclic Carbene Stabilized Silyliumylidene Ion

2019 ◽  
Vol 58 (21) ◽  
pp. 14931-14937 ◽  
Author(s):  
Philipp Frisch ◽  
Tibor Szilvási ◽  
Amelie Porzelt ◽  
Shigeyoshi Inoue
Keyword(s):  
Transition Metal ◽  
Metal Carbonyl ◽  
Carbonyl Complexes ◽  
Metal Carbonyl Complexes

scholarly journals Supported cyclopentadienylmetal carbonyl complexes

1977 ◽  
Vol 140 (2) ◽  
pp. 187-193 ◽  
Author(s):  
Giuseppe Gubitosa ◽  
Hans H. Brintzinger
Keyword(s):  
Carbonyl Complexes
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