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Title: Synthesis and characterization of two polydentate pyridylamines, their acidified salts and late first-row transition metal complexes

Authors:
; ;
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1412592
Grant/Contract Number:
AC02-05CH11231
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Polyhedron
Additional Journal Information:
Journal Volume: 124; Journal Issue: C; Related Information: CHORUS Timestamp: 2017-12-11 04:15:56; Journal ID: ISSN 0277-5387
Publisher:
Elsevier
Country of Publication:
United Kingdom
Language:
English

Citation Formats

Tsai, Yi-Ju, Lee, Una H., and Zhao, Qinliang. Synthesis and characterization of two polydentate pyridylamines, their acidified salts and late first-row transition metal complexes. United Kingdom: N. p., 2017. Web. doi:10.1016/j.poly.2016.12.021.
Tsai, Yi-Ju, Lee, Una H., & Zhao, Qinliang. Synthesis and characterization of two polydentate pyridylamines, their acidified salts and late first-row transition metal complexes. United Kingdom. doi:10.1016/j.poly.2016.12.021.
Tsai, Yi-Ju, Lee, Una H., and Zhao, Qinliang. Wed . "Synthesis and characterization of two polydentate pyridylamines, their acidified salts and late first-row transition metal complexes". United Kingdom. doi:10.1016/j.poly.2016.12.021.
@article{osti_1412592,
title = {Synthesis and characterization of two polydentate pyridylamines, their acidified salts and late first-row transition metal complexes},
author = {Tsai, Yi-Ju and Lee, Una H. and Zhao, Qinliang},
abstractNote = {},
doi = {10.1016/j.poly.2016.12.021},
journal = {Polyhedron},
number = C,
volume = 124,
place = {United Kingdom},
year = {Wed Mar 01 00:00:00 EST 2017},
month = {Wed Mar 01 00:00:00 EST 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1016/j.poly.2016.12.021

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  • Three new lanthanide metal polysulfides have been synthesized in supercritical ammonia: [Yb(NH{sub 3}){sub 8}][Cu(S{sub 4}){sub 2}]{center_dot} NH{sub 3} (I), [Yb(NH{sub 3}){sub 8}][Ag(S{sub 4}){sub 2}]{center_dot}2NH{sub 3} (II), [La(NH{sub 3}){sub 9}][Cu(S{sub 4}){sub 2}] (III). Compounds were prepared in sealed quartz tubes which were filled to one-third volume with liquid ammonia and heated at 170 {degrees}C for 3 days. Compounds I and II were obtained from the reaction of a premade ytterbium polysulfide with M and S in the ratio of 1:1:4, while [La(NH{sub 3}){sub 9}][Cu(S{sub 4}){sub 2}], III, was obtained by reacting La, Cu and S in the ratio of 1:1:8. Inmore » all these compounds, the lanthanide cation is coordinated only by ammonia, while the M{sup +} is chelated by S{sub 4}{sup 2-} to form metal tetrasulfide rings. [Yb(NH{sub 3}){sub 8}][Cu(S{sub 4}){sub 2}]{center_dot}NH{sub 3} and [Yb(NH{sub 3}){sub 8}][Ag(S{sub 4}){sub 2}]{center_dot}2NH{sub 3} contain [M(S{sub 4}){sub 2}]{sup 3-} anionic units with M{sup +} in a distorted tetrahedral coordination environment chelated by two S{sub 4}{sup 2-} groups. Compound III, [La(NH{sub 3}){sub 9}][Cu-(S{sub 4}){sub 2}], also contains anionic [Cu (S{sub 4}){sub 2}]{sup 3-} units; however, Cu{sup +} is in a trigonal planar coordination geometry due to the presence of one monodentate S{sub 4}{sup 2-}. All the compounds are unstable with respect to loss of ammonia, and decomposition yielded known ternary and binary phases.« less
  • Herein, we present the systematic, comparative computational study of the d − d transitions in a series of first row transition metal hexaaqua complexes, [M(H{sub 2}O){sub 6}]{sup n+} (M{sup 2+/3+} = V {sup 2+/3+}, Cr{sup 2+/3+}, Mn{sup 2+/3+}, Fe{sup 2+/3+}, Co{sup 2+/3+}, Ni{sup 2+}) by the means of Time-dependent Density Functional Theory (TD-DFT) and Ligand Field Density Functional Theory (LF-DFT). Influence of various exchange-correlation (XC) approximations have been studied, and results have been compared to the experimental transition energies, as well as, to the previous high-level ab initio calculations. TD-DFT gives satisfactory results in the cases of d{sup 2}, d{supmore » 4}, and low-spin d{sup 6} complexes, but fails in the cases when transitions depend only on the ligand field splitting, and for states with strong character of double excitation. LF-DFT, as a non-empirical approach to the ligand field theory, takes into account in a balanced way both dynamic and non-dynamic correlation effects and hence accurately describes the multiplets of transition metal complexes, even in difficult cases such as sextet-quartet splitting in d{sup 5} complexes. Use of the XC functionals designed for the accurate description of the spin-state splitting, e.g., OPBE, OPBE0, or SSB-D, is found to be crucial for proper prediction of the spin-forbidden excitations by LF-DFT. It is shown that LF-DFT is a valuable alternative to both TD-DFT and ab initio methods.« less
  • This study shows, for the first time, that proteins can be cross-linked selectively via transition-metal compounds to form stable protein complexes. Incubation of horse cytochrome c (designated cyt) with reagents PtCl4S with trans-(Pt(2-Fpy)2Cl2) under mild conditions yields stable diprotein complexes trans-(PtCl2(cyt)2) and trans-(Pt(2-Fpy)2(cyt)2), respectively (2-Fpy is 2-fluoropyridine). The complexes are purified and characterized chromatographically. The protein molecules are coordinated to the Pt(II) atom through the thioether side chains of their respective Met 65 residues. Spectroscopic and electrochemical measurements indicate that, except for the slightly increased abundance of the high-spin form of ferriheme, the structural and redox properties of the cytochromemore » c molecules remain unaltered upon cross linking. The diprotein complexes are stable indefinitely under ordinary conditions and yet they can be cleaved, and the native protein restored, in a mild reaction. Platinum compounds hold promise as selective and versatile reagents for cross-linking of proteins. 54 references, 1 figure, 3 tables.« less