Conformational Diversity in (Octaethylporphinato) (trichloroacetato)iron(III) Derivatives

PDF Version Also Available for Download.

Description

Treatment of [Fe(OEP)]20 with trichloroacetic acid results in ruffled formation of (octaethylporphinato trichloroacetato)iron(HI). Various crystalline solvates can be isolated, depending on the crystallization solvent. Initial crystallization with CHC13/hexanes resulted in the isolation of an unsolvated form. [Fe(OEP)(02C2C13 )]. This form contains distinct porphyrin core conformations at the same site: one is domed and the other is ruffled. Crystal data for [Fe(OEP)(02C2C13 )]: Q = 14.734(4) .4. b = 13.674(1) .\. c = 17..541 [,.5] .~. 3 = 90.67(1)0, V = 35-!5.8(14) .\3. monoclinic. space group R1/ n. Z = 4. Subsequent crystallization with CHC13/hexanes resulted in a new crystalline form, ... continued below

Creation Information

Cheng, B.; Ma, J.; Neal, T.J.; Scheidt, W.R.; Schulz, C.E. & Shelnutt, J.A. October 19, 1998.

Context

This article is part of the collection entitled: Office of Scientific & Technical Information Technical Reports and was provided by UNT Libraries Government Documents Department to Digital Library, a digital repository hosted by the UNT Libraries. More information about this article can be viewed below.

Who

People and organizations associated with either the creation of this article or its content.

Publisher

  • Sandia National Laboratories
    Publisher Info: Sandia National Laboratories, Albuquerque, NM, and Livermore, CA
    Place of Publication: Albuquerque, New Mexico

Provided By

UNT Libraries Government Documents Department

Serving as both a federal and a state depository library, the UNT Libraries Government Documents Department maintains millions of items in a variety of formats. The department is a member of the FDLP Content Partnerships Program and an Affiliated Archive of the National Archives.

Contact Us

What

Descriptive information to help identify this article. Follow the links below to find similar items on the Digital Library.

Description

Treatment of [Fe(OEP)]20 with trichloroacetic acid results in ruffled formation of (octaethylporphinato trichloroacetato)iron(HI). Various crystalline solvates can be isolated, depending on the crystallization solvent. Initial crystallization with CHC13/hexanes resulted in the isolation of an unsolvated form. [Fe(OEP)(02C2C13 )]. This form contains distinct porphyrin core conformations at the same site: one is domed and the other is ruffled. Crystal data for [Fe(OEP)(02C2C13 )]: Q = 14.734(4) .4. b = 13.674(1) .\. c = 17..541 [,.5] .~. 3 = 90.67(1)0, V = 35-!5.8(14) .\3. monoclinic. space group R1/ n. Z = 4. Subsequent crystallization with CHC13/hexanes resulted in a new crystalline form, [Fe(OEP)(OzC2C13 )~.- CHC13; the porphyrin core is slightly ruffled. Crystal data for [Fe(OEP)(OoC2C13 )]. CHC13: a =12.323(1) .~, 6 = 13.062(3) .\. C = 14.327(2) .$, Q = 89.32(1)", .3 = 113.36(2)0. :~ = 105.26(1)'. V = `2031.3(6) .\3. triclinic. space group Pi. Z = 2. Crystallization with CH2C12/hexanes resulted in the isolation of yet another form, [Fe(OEP) (02 C2C13)]. H02C2C13. which contains two independent molecules in the unit cell: molecule is slightly saddled and molecule B is modestly ruffled. Crystal data for [Fe(OEP)(02ClC13 )]. H02C2C13: a = 13.148(3) .\, b = 13.45.5(3) A, c = Q3.761(5) -& ~ = 90.72(3)", ~ = 91. ~4(3)". -y = 92.36(3)0, V = 4198.5(15) .\3, triclinic.space group PI, Z = 4. .+11 conformations form dimers in the solid state. Temperature-dependent manometic susceptibility measurements showed that [Fe(OEP)(02C2C13)] .CHC13 contains a high-spin iron(III) center; the data for {Fe(OEP)(02C2C13 )l.H02C2C13 are understood in terms of an admixed intermediate-spin state (S = 3/2, 5/2) and are readily fit to a faltempo model with a ground state multiplet containing about 78% S = 5/2 character and 22% S = 3/2 character. The structural data for [Fe(OEP)(02C2C13 )]. CHC13 are consistent with the observed high-spin state, while data for ~Fe(OEP) (02 C2C13)] .H02C2C13 are consistent with the admixed-spin iron(HI) character. The observed core conformations have been described by a normal-coordinate structural decomposition method.

Subjects

Source

  • Journal Name: Inorganic Chemistry Acta

Language

Item Type

Identifier

Unique identifying numbers for this article in the Digital Library or other systems.

  • Other: DE00001082
  • Report No.: SAND98-2353J
  • Grant Number: NONE
  • Office of Scientific & Technical Information Report Number: 1082
  • Archival Resource Key: ark:/67531/metadc618452

Collections

This article is part of the following collection of related materials.

Office of Scientific & Technical Information Technical Reports

Reports, articles and other documents harvested from the Office of Scientific and Technical Information.

Office of Scientific and Technical Information (OSTI) is the Department of Energy (DOE) office that collects, preserves, and disseminates DOE-sponsored research and development (R&D) results that are the outcomes of R&D projects or other funded activities at DOE labs and facilities nationwide and grantees at universities and other institutions.

What responsibilities do I have when using this article?

When

Dates and time periods associated with this article.

Creation Date

  • October 19, 1998

Added to The UNT Digital Library

  • June 16, 2015, 7:43 a.m.

Description Last Updated

  • Nov. 23, 2016, 11:24 a.m.

Usage Statistics

When was this article last used?

Yesterday: 0
Past 30 days: 0
Total Uses: 3

Interact With This Article

Here are some suggestions for what to do next.

Start Reading

PDF Version Also Available for Download.

Citations, Rights, Re-Use

Cheng, B.; Ma, J.; Neal, T.J.; Scheidt, W.R.; Schulz, C.E. & Shelnutt, J.A. Conformational Diversity in (Octaethylporphinato) (trichloroacetato)iron(III) Derivatives, article, October 19, 1998; Albuquerque, New Mexico. (digital.library.unt.edu/ark:/67531/metadc618452/: accessed November 24, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.