Comparative Reactivity of Sterically Crowded nf3(C5Me5)3Nd and (C5Me5)3U Complexes with CO:  Formation of a Nonclassical Carbonium Ion versus an f Element Metal Carbonyl Complex

2003 ◽  
Vol 125 (45) ◽  
pp. 13831-13835 ◽  
Author(s):  
William J. Evans ◽  
Stosh A. Kozimor ◽  
Gregory W. Nyce ◽  
Joseph W. Ziller
Keyword(s):  
Metal Carbonyl ◽  
Carbonyl Complex ◽  
Carbonium Ion ◽  
Comparative Reactivity

Carbon Chain Growth by Sequential Reactions of CO and CO2 with a Transition Metal Carbonyl Complex

2018 ◽  
Author(s):  
Richard Kong ◽  
Mark Crimmin
Keyword(s):  
Transition Metal ◽  
Metal Carbonyl ◽  
Carbon Chain ◽  
Chain Growth ◽  
Carbonyl Complex ◽  
Fischer Tropsch ◽  
Carbon Chains ◽  
Sequential Coupling ◽  
Energy Economy ◽  
Sequential Reactions

<i>The formation of carbon chains by the coupling of COx (X = 1 or 2) units on transition metals is a fundamental step relevant to Fischer-Tropsch catalysis. Fischer-Tropsch catalysis produces energy dense liquid hydrocarbons from synthesis gas (CO and H2) and has been a mainstay of the energy economy since its discovery nearly a century ago. Despite detailed studies aimed at elucidating the steps of catalysis, experimental evidence for chain growth (Cn to Cn+1 ; n > 2) from the reaction of CO with metal complexes is unprecedented. In this paper, we show that carbon chains can be grown from sequential reactions of CO or CO2 with a transition metal carbonyl complex. By exploiting the cooperative effect of transition and main group metals, we document the first example of chain propagation from sequential coupling of CO units (C1 to C3 to C4), along with the first example of incorporation of CO2 into the growing carbon chain.</i><br>

scholarly journals The influence of chemical parameters on the in-situ metal carbonyl complex formation studied with the fast on-line reaction apparatus (FORA)

2021 ◽  
Vol 109 (4) ◽  
pp. 243-260 ◽  
Author(s):  
Yves Wittwer ◽  
Robert Eichler ◽  
Dominik Herrmann ◽  
Andreas Türler
Keyword(s):  
Metal Carbonyl ◽  
Ambient Air ◽  
Single Atom ◽  
Carbonyl Complex ◽  
Carbonyl Complexes ◽  
On Line ◽  
Carrier Gases ◽  
And Performance ◽  
Atom Chemistry

Abstract A new setup named Fast On-line Reaction Apparatus (FORA) is presented which allows for the efficient investigation and optimization of metal carbonyl complex (MCC) formation reactions under various reaction conditions. The setup contains a 252Cf-source producing short-lived Mo, Tc, Ru and Rh isotopes at a rate of a few atoms per second by its 3% spontaneous fission decay branch. Those atoms are transformed within FORA in-situ into volatile metal carbonyl complexes (MCCs) by using CO-containing carrier gases. Here, the design, operation and performance of FORA is discussed, revealing it as a suitable setup for performing single-atom chemistry studies. The influence of various gas-additives, such as CO2, CH4, H2, Ar, O2, H2O and ambient air, on the formation and transport of MCCs was investigated. O2, H2O and air were found to harm the formation and transport of MCCs in FORA, with H2O being the most severe. An exception is Tc, for which about 130 ppmv of H2O caused an increased production and transport of volatile compounds. The other gas-additives were not influencing the formation and transport efficiency of MCCs. Using an older setup called Miss Piggy based on a similar working principle as FORA, it was additionally investigated if gas-additives are mostly affecting the formation or only the transport stability of MCCs. It was found that mostly formation is impacted, as MCCs appear to be much less sensitive to reacting with gas-additives in comparison to the bare Mo, Tc, Ru and Rh atoms.

scholarly journals The influence of physical parameters on the in-situ metal carbonyl complex formation studied with the Fast On-line Reaction Apparatus (FORA)

2021 ◽  
Vol 109 (4) ◽  
pp. 261-281
Author(s):  
Yves Wittwer ◽  
Robert Eichler ◽  
Dominik Herrmann ◽  
Andreas Türler
Keyword(s):  
Gas Flow ◽  
Metal Carbonyl ◽  
Fission Products ◽  
Reaction Chamber ◽  
Single Atom ◽  
Physical Parameters ◽  
Carbonyl Complex ◽  
Reaction Conditions ◽  
On Line ◽  
The Impact

Abstract The Fast On-line Reaction Apparatus (FORA) was used to investigate the influence of various reaction parameters onto the formation and transport of metal carbonyl complexes (MCCs) under single-atom chemistry conditions. FORA is based on a 252Cf-source producing short-lived Mo, Tc, Ru and Rh isotopes. Those are recoiling from the spontaneous fission source into a reaction chamber flushed with a gas-mixture containing CO. Upon contact with CO, fission products form volatile MCCs which are further transported by the gas stream to the detection setup, consisting of a charcoal trap mounted in front of a HPGe γ-detector. Depending on the reaction conditions, MCCs are formed and transported with different efficiencies. Using this setup, the impact of varying physical parameters like gas flow, gas pressure, kinetic energy of fission products upon entering the reaction chamber and temperature of the reaction chamber on the formation and transport yields of MCCs was investigated. Using a setup similar to FORA called Miss Piggy, various gas mixtures of CO with a selection of noble gases, as well as N2 and H2, were investigated with respect to their effect onto MCC formation and transport. Based on this measurements, optimized reaction conditions to maximize the synthesis and transport of MCCs are suggested. Explanations for the observed results supported by simulations are suggested as well.

scholarly journals Diminished viability of human ovarian cancer cells by antigen-specific delivery of carbon monoxide with a family of photoactivatable antibody-photoCORM conjugates

2020 ◽  
Vol 11 (2) ◽  
pp. 467-473 ◽  
Author(s):  
Brian Kawahara ◽  
Lucy Gao ◽  
Whitaker Cohn ◽  
Julian P. Whitelegge ◽  
Suvajit Sen ◽  
...  
Keyword(s):  
Ovarian Cancer ◽  
Carbon Monoxide ◽  
Transition Metal ◽  
Cancer Cells ◽  
Metal Carbonyl ◽  
Ovarian Cancer Cells ◽  
Human Ovarian Cancer ◽  
Carbonyl Complex

Antibodies conjugated to a photoactive transition metal carbonyl complex afford antigen-directed delivery of cytotoxic carbon monoxide to ovarian cancer cells.

ChemInform Abstract: A TRANSITION-METAL CARBONYL COMPLEX OF PENTALENE

1973 ◽  
Vol 4 (52) ◽  
pp. no-no
Author(s):  
A. BROOKES ◽  
J. HOWARD ◽  
S. A. R. KNOX ◽  
F. G. A. STONE ◽  
P. WOODWARD
Keyword(s):  
Transition Metal ◽  
Metal Carbonyl ◽  
Carbonyl Complex

Photoreduction of CO to Methanol. The Photolysis of Aqueous Solutions of [Os(NH3)5(CO)]2+

2013 ◽  
Vol 68 (12) ◽  
pp. 1371-1374
Author(s):  
Horst Kunkely ◽  
Arnd Vogler
Keyword(s):  
Aqueous Solution ◽  
Aqueous Solutions ◽  
Artificial Photosynthesis ◽  
Metal Carbonyl ◽  
Carbonyl Complex ◽  
Carbonyl Complexes ◽  
Metal Carbonyl Complexes

The carbonyl complex [OsII(NH3)5(CO)]2+ undergoes a photolysis in aqueous solution which yields [OsVI(NH3)4N]3+ (Φ=10-3 at λirr =255 nm) and methanol. This photoreduction of CO to CH3OH represents a novel type of photoreactivity of metal carbonyl complexes and could be utilized for an artificial photosynthesis

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