FRINK Linked Data Fragments server

Matches in SemOpenAlex for { <https://semopenalex.org/work/W2081142715> ?p ?o ?g. }

• W2081142715 endingPage "6578" @default.
• W2081142715 startingPage "6564" @default.
• W2081142715 abstract "Three bis-axially ligated complexes of iron(III) octaethyltetraphenylporphyrin, (OETPP)Fe(III), have been prepared, which are low-spin complexes, each with two axial nitrogen-donor ligands (N-methylimidazole (N-MeIm), 4-(dimethylamino)pyridine (4-NMe(2)Py), and 2-methylimidazole (2-MeImH)). The crystal and molecular structure of the bis-(2-MeImH) complex shows the macrocycle to be in a saddled conformation, with the ligands in perpendicular planes aligned at 14 degrees to the porphyrin nitrogens so as to relieve the steric interaction between the 2-methyl groups and the porphyrin. The Fe-N(por) bond lengths are typical of nonplanar six-coordinate low-spin Fe(III) complexes, while the axial Fe-N(ax) bond lengths are substantially longer than those of [(TPP)Fe(2-MeImH)(2)](+) (2.09(2) A as compared to 2.015(4) and 2.010(4) A). The crystal and molecular structure of the bis-(4-NMe(2)Py) complex also shows the macrocycle to be in a mainly saddled conformation, but with a significant ruffled component. As a result, the average Fe-N(por) bonds are significantly shorter (1.951 A as compared to 1.974 A) than those of the bis-(2-MeImH) complex. One ligand is aligned at 9 degrees to two trans porphyrin nitrogens, while the other is at 79 degrees to the same porphyrin nitrogens, producing a dihedral angle of 70 degrees between the ligand planes. The EPR spectrum of this complex, like that of the bis-(2-MeImH) complex, is of the large g(max) type, with g(max) = 3.29 and 3.26, respectively. However, in frozen CD(2)Cl(2), [(OETPP)Fe(N-MeIm)(2)](+) exhibits both large g(max) and normal rhombic signals, suggesting the presence of both perpendicular and parallel ligand orientations. The 1- and 2D (1)H NMR spectra of each of these complexes, as well as the chloroiron(III) starting material, were investigated as a function of temperature. The COSY and NOESY/EXSY spectra of the chloride complex are consistent with the expected J-coupling and saddle inversion dynamics, respectively. Complete spectral assignments for the bis-(N-MeIm) and -(4-NMe(2)Py) complexes have been made using 2D (1)H NMR techniques. In each case, the number of resonances due to methylene (two) and phenyl protons (one each) is consistent with D(2)(d)() symmetry, and therefore an effective perpendicular orientation of the axial ligands on the time scale of the NMR experiments. The temperature dependences of the (1)H resonances of these complexes show significant deviations from Curie behavior, and also evidence of extensive ligand exchange and rotation. Spectral assignment of the eight methylene resonances of the bis-(2-MeImH) complex to the four ethyl groups was possible through the use of 2D (1)H NMR techniques. The complex is fluxional, even at -90 degrees C, and ROESY data suggest that the predominant process is saddle inversion accompanied by simultaneous rotation of the axial ligands. Saddle inversion becomes slow on the 2D NMR time scale as the temperature is lowered in the ligand order of N-MeIm > 4-NMe(2)Py > 2-MeImH, probably due mainly to progressive destabilization of the ground state rather than progressive stabilization of the transition state of the increasingly hindered bis-ligand complexes." @default.
• W2081142715 created "2016-06-24" @default.
• W2081142715 creator A5007172461 @default.
• W2081142715 creator A5022854842 @default.
• W2081142715 creator A5029303492 @default.
• W2081142715 creator A5046963553 @default.
• W2081142715 creator A5049293749 @default.
• W2081142715 creator A5050533134 @default.
• W2081142715 creator A5072559840 @default.
• W2081142715 creator A5082370979 @default.
• W2081142715 date "2001-06-13" @default.
• W2081142715 modified "2023-10-06" @default.
• W2081142715 title "Molecular Structures and Magnetic Resonance Spectroscopic Investigations of Highly Distorted Six-Coordinate Low-Spin Iron(III) Porphyrinate Complexes" @default.
• W2081142715 cites W1516240255 @default.
• W2081142715 cites W1522211358 @default.
• W2081142715 cites W1770951852 @default.
• W2081142715 cites W1967772383 @default.
• W2081142715 cites W1969087107 @default.
• W2081142715 cites W1973358223 @default.
• W2081142715 cites W1974246849 @default.
• W2081142715 cites W1979282932 @default.
• W2081142715 cites W1982371246 @default.
• W2081142715 cites W1982712514 @default.
• W2081142715 cites W1984052240 @default.
• W2081142715 cites W1986463221 @default.
• W2081142715 cites W1986468006 @default.
• W2081142715 cites W1988862066 @default.
• W2081142715 cites W1990245590 @default.
• W2081142715 cites W1991979924 @default.
• W2081142715 cites W1997162815 @default.
• W2081142715 cites W1998636296 @default.
• W2081142715 cites W2000717366 @default.
• W2081142715 cites W2005142839 @default.
• W2081142715 cites W2006106417 @default.
• W2081142715 cites W2009860588 @default.
• W2081142715 cites W2015033155 @default.
• W2081142715 cites W2016018644 @default.
• W2081142715 cites W2018339708 @default.
• W2081142715 cites W2018598267 @default.
• W2081142715 cites W2019149466 @default.
• W2081142715 cites W2019573268 @default.
• W2081142715 cites W2020520553 @default.
• W2081142715 cites W2020849992 @default.
• W2081142715 cites W2022916467 @default.
• W2081142715 cites W2022988636 @default.
• W2081142715 cites W2028825292 @default.
• W2081142715 cites W2032347469 @default.
• W2081142715 cites W2032355835 @default.
• W2081142715 cites W2034627389 @default.
• W2081142715 cites W2036342159 @default.
• W2081142715 cites W2041178006 @default.
• W2081142715 cites W2046556962 @default.
• W2081142715 cites W2053372707 @default.
• W2081142715 cites W2053848380 @default.
• W2081142715 cites W2054682788 @default.
• W2081142715 cites W2056219044 @default.
• W2081142715 cites W2061245515 @default.
• W2081142715 cites W2062446565 @default.
• W2081142715 cites W2063232817 @default.
• W2081142715 cites W2068100549 @default.
• W2081142715 cites W2068337018 @default.
• W2081142715 cites W2070562252 @default.
• W2081142715 cites W2073047726 @default.
• W2081142715 cites W2074108235 @default.
• W2081142715 cites W2084582102 @default.
• W2081142715 cites W2085102778 @default.
• W2081142715 cites W2087460952 @default.
• W2081142715 cites W2103604301 @default.
• W2081142715 cites W2130271590 @default.
• W2081142715 cites W2153197177 @default.
• W2081142715 cites W2169791789 @default.
• W2081142715 cites W2170621128 @default.
• W2081142715 cites W2170670145 @default.
• W2081142715 cites W2494367561 @default.
• W2081142715 cites W7827006 @default.
• W2081142715 doi "https://doi.org/10.1021/ja004053s" @default.
• W2081142715 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/11439043" @default.
• W2081142715 hasPublicationYear "2001" @default.
• W2081142715 type Work @default.
• W2081142715 sameAs 2081142715 @default.
• W2081142715 citedByCount "70" @default.
• W2081142715 countsByYear W20811427152012 @default.
• W2081142715 countsByYear W20811427152013 @default.
• W2081142715 countsByYear W20811427152014 @default.
• W2081142715 countsByYear W20811427152015 @default.
• W2081142715 countsByYear W20811427152016 @default.
• W2081142715 countsByYear W20811427152017 @default.
• W2081142715 countsByYear W20811427152018 @default.
• W2081142715 countsByYear W20811427152020 @default.
• W2081142715 countsByYear W20811427152021 @default.
• W2081142715 countsByYear W20811427152022 @default.
• W2081142715 countsByYear W20811427152023 @default.
• W2081142715 crossrefType "journal-article" @default.
• W2081142715 hasAuthorship W2081142715A5007172461 @default.
• W2081142715 hasAuthorship W2081142715A5022854842 @default.
• W2081142715 hasAuthorship W2081142715A5029303492 @default.
• W2081142715 hasAuthorship W2081142715A5046963553 @default.
• W2081142715 hasAuthorship W2081142715A5049293749 @default.

• next