Correction to “Identification of the Non-Pertechnetate Species in Hanford Waste Tanks, Tc(I)–Carbonyl Complexes”

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.

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

Inorganic Chemistry ◽

10.1021/acs.inorgchem.9b02772 ◽

2019 ◽

Vol 58 (21) ◽

pp. 14931-14937 ◽

Cited By ~ 6

Author(s):

Philipp Frisch ◽

Tibor Szilvási ◽

Amelie Porzelt ◽

Shigeyoshi Inoue

Keyword(s):

Transition Metal ◽

Metal Carbonyl ◽

Carbonyl Complexes ◽

Metal Carbonyl Complexes

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Supported cyclopentadienylmetal carbonyl complexes

Journal of Organometallic Chemistry ◽

10.1016/s0022-328x(00)93194-2 ◽

1977 ◽

Vol 140 (2) ◽

pp. 187-193 ◽

Cited By ~ 9

Author(s):

Giuseppe Gubitosa ◽

Hans H. Brintzinger

Keyword(s):

Carbonyl Complexes

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

Radiochimica Acta ◽

10.1515/ract-2020-0031 ◽

2021 ◽

Vol 109 (4) ◽

pp. 243-260 ◽

Cited By ~ 1

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.

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