|
|
|
|
| LEADER |
01000naa a22002652 4500 |
| 001 |
NLM217141552 |
| 003 |
DE-627 |
| 005 |
20231224033401.0 |
| 007 |
cr uuu---uuuuu |
| 008 |
231224s2012 xx |||||o 00| ||eng c |
| 024 |
7 |
|
|a 10.1002/jcc.22978
|2 doi
|
| 028 |
5 |
2 |
|a pubmed24n0723.xml
|
| 035 |
|
|
|a (DE-627)NLM217141552
|
| 035 |
|
|
|a (NLM)22517297
|
| 040 |
|
|
|a DE-627
|b ger
|c DE-627
|e rakwb
|
| 041 |
|
|
|a eng
|
| 100 |
1 |
|
|a Tang, Hao
|e verfasserin
|4 aut
|
| 245 |
1 |
0 |
|a Comparison of the FeO(2+) and FeS(2+) complexes in the cyanide and isocyanide ligand environment for methane hydroxylation
|
| 264 |
|
1 |
|c 2012
|
| 336 |
|
|
|a Text
|b txt
|2 rdacontent
|
| 337 |
|
|
|a ƒaComputermedien
|b c
|2 rdamedia
|
| 338 |
|
|
|a ƒa Online-Ressource
|b cr
|2 rdacarrier
|
| 500 |
|
|
|a Date Completed 30.06.2015
|
| 500 |
|
|
|a Date Revised 01.05.2015
|
| 500 |
|
|
|a published: Print-Electronic
|
| 500 |
|
|
|a Citation Status PubMed-not-MEDLINE
|
| 520 |
|
|
|a Copyright © 2012 Wiley Periodicals, Inc.
|
| 520 |
|
|
|a A general comparison of fundamental distinctions between the FeO(2+) and FeS(2+) complexes in an identical cyanide or isocyanide ligand environment for methane hydroxylation has been probed computationally in this work in a series of hypothetical [Fe(IV)(X)(CN)5](3-), [Fe(IV)(X)(NC)5](3-), (X = O, S) complexes. We have detailed an analysis of the geometric and electronic structures using density functional theory calculations. In addition, their σ- and π-mechanisms in C-H bond activation process have been described with the aid of the schematic molecular orbital diagram. From our theoretical results, it is shown that (a) the iron(IV)-sulfido complex apparently is able to hydroxylate C-H bond of methane as good as the iron(IV)-oxo species, (b) the O-CN, S-CN complexes have an inherent preference for the low-spin state, while for the case of O-NC and S-NC in which S = 1 and S = 2 states are relatively close in energy, (c) each of the d block electron orbital plays an important role, which is not just spectator electron, and (d) in comparison to the cyanide and isocyanide ligand environment, we can see that the FeS(2+) species prefer the cyanide ligand environment, while the FeO(2+) species favor the isocyanide ligand environment. In addition, a remarkably good correlation of the σ-/π-mechanism for hydrogen abstraction from methane with the gap between the Fe-dz2 (α) and C-H (α) pair as well as the Fe-dxz/yz (β) and C-H (β) pair has been found
|
| 650 |
|
4 |
|a Journal Article
|
| 650 |
|
4 |
|a FeO2+
|
| 650 |
|
4 |
|a FeS2+
|
| 650 |
|
4 |
|a cyanide or isocyanide ligand environment
|
| 650 |
|
4 |
|a methane hydroxylation
|
| 650 |
|
4 |
|a σ‐ and π‐mechanisms
|
| 700 |
1 |
|
|a Li, Zhuo
|e verfasserin
|4 aut
|
| 700 |
1 |
|
|a Yang, Yu-Hong
|e verfasserin
|4 aut
|
| 700 |
1 |
|
|a Zhao, Ying
|e verfasserin
|4 aut
|
| 700 |
1 |
|
|a Wan, Su-Qin
|e verfasserin
|4 aut
|
| 700 |
1 |
|
|a Liu, Hui-Ling
|e verfasserin
|4 aut
|
| 700 |
1 |
|
|a Huang, Xu-Ri
|e verfasserin
|4 aut
|
| 773 |
0 |
8 |
|i Enthalten in
|t Journal of computational chemistry
|d 1984
|g 33(2012), 16 vom: 15. Juni, Seite 1448-57
|w (DE-627)NLM098138448
|x 1096-987X
|7 nnns
|
| 773 |
1 |
8 |
|g volume:33
|g year:2012
|g number:16
|g day:15
|g month:06
|g pages:1448-57
|
| 856 |
4 |
0 |
|u http://dx.doi.org/10.1002/jcc.22978
|3 Volltext
|
| 912 |
|
|
|a GBV_USEFLAG_A
|
| 912 |
|
|
|a SYSFLAG_A
|
| 912 |
|
|
|a GBV_NLM
|
| 912 |
|
|
|a GBV_ILN_350
|
| 951 |
|
|
|a AR
|
| 952 |
|
|
|d 33
|j 2012
|e 16
|b 15
|c 06
|h 1448-57
|