The tris(oxalato)cobaltate(III) complex [Co(C(2)O(4))(3)](3-), E(o)(Co)(III/II)=+0.57 V) is readily reduced by the 2e(-) reagents, Sn(II) and Ge(II), in contrast to (NH(3))(5)CoCl(2+) and (NH(3))(5)CoBr(2+), which are unreactive toward these donors. Rates for the oxalato oxidant are only 10(-3)-10(-2) as great as those for vitamin B(12a)(aquacob(III)alamin, E(o)+0.35 V at pH 1), in accord with the suggestion that reductions of corrin-bound cobalt(III) by Sn(II) and Ge(II) occur predominantly through an additional path involving Co(i). Reductions of the oxalato complex by 2e(-) donors are taken to proceed by initial formation of odd-electron intermediates (e.g., Sn(III) and Ge(III)) which react rapidly with Co(III). Such a two-step sequence is in keeping with the observed behavior of the rare reductant, Ti(II), which is found to be oxidized by [Co(C(2)O(4))(3)](3-) more slowly than (independently prepared) Ti(III) under comparable conditions.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1039/B408758P | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Hybrid Iodide Perovskites of Divalent Alkaline Earth and Lanthanide Elements.
J Am Chem Soc
December 2023
Materials Department and Materials Research Laboratory, University of California, Santa Barbara, California 93106, United States.
Hybrid halide perovskites AMX (A = ammonium cation, M = divalent cation, X = Cl, Br, I) have been extensively studied but have only previously been reported for the divalent carbon group elements Ge, Sn, and Pb. While they have displayed an impressive range of optoelectronic properties, the instability of Ge and Sn and the toxicity of Pb have stimulated significant interest in finding alternatives to these carbon group-based perovskites. Here, we describe the low-temperature solid-state synthesis of five new hybrid iodide perovskites centered around divalent alkaline earth and lanthanide elements, with the general formula AMI (A = methylammonium, MA; M = Sr, Sm, Eu, and A = formamidinium, FA; M = Sr, Eu).
View Article and Find Full Text PDFRearrangement of a Ge(II) aryloxide to yield a new Ge(II) oxo-cluster [Ge(μ-O)(μ-OCH-2,4,6-Cy)](NH): main group aryloxides of Ge(II), Sn(II), and Pb(II) [M(OCH-2,4,6-Cy)] (Cy = cyclohexyl).
Dalton Trans
July 2023
Department of Chemistry, University of California, Davis, California 95616, USA.
The new Ge(II) cluster [Ge(μ-O)(μ-OCH-2,4,6-Cy)](NH) (1) and three divalent Group 14 aryloxide derivatives [Ge(OCH-2,4,6-Cy)] (2), [Sn(OCH-2,4,6-Cy)] (3), and [Pb(OCH-2,4,6-Cy)] (4) of the new tricyclohexylphenyloxo ligand, [(-OCH-2,4,6-Cy)] (Cy = cyclohexyl), were synthesized and characterized. Complexes 1-4 were obtained by reaction of the metal bissilylamides M(N(SiMe)) (M = Ge, Sn, Pb) with 2,4,6-tricyclohexylphenol in hexane at room temperature. If the freshly generated reaction mixture for the synthesis of 2 is stirred in solution for 12 h at room temperature, the cluster [Ge(μ-O)(μ-OCH-2,4,6-Cy)](NH) (1), which features a rare GeO core that includes ammonia molecules in non-coordinating positions, is formed.
View Article and Find Full Text PDFIntrinsic Formamidinium Tin Iodide Nanocrystals by Suppressing the Sn(IV) Impurities.
Nano Lett
March 2023
Institute of Inorganic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zürich, CH-8093 Zürich, Switzerland.
The long search for nontoxic alternatives to lead halide perovskites (LHPs) has shown that some compelling properties of LHPs, such as low effective masses of carriers, can only be attained in their closest Sn(II) and Ge(II) analogues, despite their tendency toward oxidation. Judicious choice of chemistry allowed formamidinium tin iodide (FASnI) to reach a power conversion efficiency of 14.81% in photovoltaic devices.
View Article and Find Full Text PDFChemistry of the Bis(imine)-Based Tetradentate Ligand Stabilized Group 14 E(II) Cations (E=Ge and Sn).
Chem Rec
May 2022
Department of Chemistry, Indian Institute of Science Education and Research, Pune, Dr. Homi Bhabha Road, Pashan, Pune, 411008, Maharashtra, India.
The ambiphilic Ge(II) and Sn(II) cationic species have been reported to be isolated through kinetic or thermodynamic stabilizations. Nonetheless, steric congestion or excessive coordination of donor atoms to the cationic center concurrently disfavors its prompt reactivity. Our research in this field revolves around the utilization of structurally non-rigid bis(imine) based tetradentate supporting ligands for the stabilization of Ge(II) and Sn(II) cationic species.
View Article and Find Full Text PDFPyridylpyrrolido ligand in Ge(II) and Sn(II) chemistry: synthesis, reactivity and catalytic application.
Dalton Trans
November 2021
Inorganic Chemistry and Catalysis Division, CSIR-National Chemical Laboratory, Dr Homi Bhabha Road, Pashan, Pune 411008, India.
In our previous communication, we have reported the synthesis of a new chlorogermylene (B) featuring a pyridylpyrrolido ligand. This study details the preparation of a series of new germylenes and stannylenes starting from B. A transmetallation reaction between B and SnCl led to the analogous chlorostannylene (1) with the simultaneous elimination of GeCl.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!