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Title: Cyanide Ligand Assembly by Carbon Atom Transfer to an Iron Nitride

Abstract

The new iron(IV) nitride complex PhB( iPr 2Im) 3Fe≡N reacts with two equivalents of bis(diisopropylamino)cyclopropenylidene (BAC) to provide PhB( iPr 2Im) 3Fe(CN)(N 2)(BAC). This unusual example of a four-electron reaction involves carbon atom transfer from BAC to create a cyanide ligand along with the alkyne iPr 2N-C≡C-N iPr 2. The iron complex is in equilibrium with an N 2- free species. Further reaction with CO leads to formation of a CO analogue, which can be independently prepared using NaCN as the cyanide source, while reaction with B(C 6F 5) 3 provides the cyanoborane derivative.

Authors:
 [1];  [1];  [2];  [1];  [1];  [1]; ORCiD logo [3]; ORCiD logo [1]
  1. Indiana Univ., Bloomington, IN (United States). Dept. of Chemistry
  2. Indiana Univ., Bloomington, IN (United States). Dept. of Chemistry; Loyola Univ., Chicago, IL (United States)
  3. Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemistry and Chemical Biology; Brandeis Univ., Waltham, MA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Indiana Univ., Bloomington, IN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1393565
Grant/Contract Number:
FG02-08ER15996; CHE-1566258; CHE-0443580
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 40; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Martinez, Jorge L., Lin, Hsiu-Jung, Lee, Wei-Tsung, Pink, Maren, Chen, Chun-Hsing, Gao, Xinfeng, Dickie, Diane A., and Smith, Jeremy M. Cyanide Ligand Assembly by Carbon Atom Transfer to an Iron Nitride. United States: N. p., 2017. Web. doi:10.1021/jacs.7b08704.
Martinez, Jorge L., Lin, Hsiu-Jung, Lee, Wei-Tsung, Pink, Maren, Chen, Chun-Hsing, Gao, Xinfeng, Dickie, Diane A., & Smith, Jeremy M. Cyanide Ligand Assembly by Carbon Atom Transfer to an Iron Nitride. United States. doi:10.1021/jacs.7b08704.
Martinez, Jorge L., Lin, Hsiu-Jung, Lee, Wei-Tsung, Pink, Maren, Chen, Chun-Hsing, Gao, Xinfeng, Dickie, Diane A., and Smith, Jeremy M. 2017. "Cyanide Ligand Assembly by Carbon Atom Transfer to an Iron Nitride". United States. doi:10.1021/jacs.7b08704.
@article{osti_1393565,
title = {Cyanide Ligand Assembly by Carbon Atom Transfer to an Iron Nitride},
author = {Martinez, Jorge L. and Lin, Hsiu-Jung and Lee, Wei-Tsung and Pink, Maren and Chen, Chun-Hsing and Gao, Xinfeng and Dickie, Diane A. and Smith, Jeremy M.},
abstractNote = {The new iron(IV) nitride complex PhB(iPr2Im)3Fe≡N reacts with two equivalents of bis(diisopropylamino)cyclopropenylidene (BAC) to provide PhB(iPr2Im)3Fe(CN)(N2)(BAC). This unusual example of a four-electron reaction involves carbon atom transfer from BAC to create a cyanide ligand along with the alkyne iPr2N-C≡C-NiPr2. The iron complex is in equilibrium with an N2- free species. Further reaction with CO leads to formation of a CO analogue, which can be independently prepared using NaCN as the cyanide source, while reaction with B(C6F5)3 provides the cyanoborane derivative.},
doi = {10.1021/jacs.7b08704},
journal = {Journal of the American Chemical Society},
number = 40,
volume = 139,
place = {United States},
year = 2017,
month = 9
}

Journal Article:
Free Publicly Available Full Text
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  • The reaction of the new carbene-containing cluster complex Os{sub 3}(CO){sub 11}(C(Et)NMe{sub 2}) (2) with PhC{triple bond}CH has yielded the complex Os{sub 3}(CO){sub 9}({mu}{sub 3}-PhC{sub 2}{l brace}C(Et)(NMe{sub 2}){r brace})({mu}-H) (3, 35%), which contains a triply bridging alkyne ligand with phenyl and ethyl(dimethyliminio)methyl substituents. The product is believed to have been formed by the transfer of the C(Et)NMe{sub 2} carbene ligand in 2 to the {alpha}-carbon atom of a bridging PhC{triple bond}C ligand in an intermediate formed by the activation of PhC{triple bond}CH by the cluster.
  • Excited-state relaxation pathways have been examined for some bi- and trinuclear transition-metal complexes containing the Ru(bpy){sub 2}{sup 2+} chromophore linked (or metalated) through cyanide to an amine chromium(III) or rhodium(III) complex. The ({sup 3}CT)Ru(bpy){sub 2}{sup 2+} absorption and emission maxima and the Ru(III)-(II) reduction potentials all increase in energy with metalation. In most instances energy migration from the initially excited ruthenium center to the acceptor metal centers occurred in discrete steps analogous to elementary chemical reactions between independent molecular species.The migration of energy was manifested by quenching of the ({sup 3}CT)Ru donor emission. This was sometimes accompanied either by ({supmore » 2}E)Cr(III) phosphorescence emission in the chromium metalates or by the growth of a metal-to-metal charge-transfer absorption in a rhodium metalate. Picosecond flash photolysis has been used to observe the equilibration (in about 1 ns) between the ({sup 3}CT)Ru(bpy){sub 2}{sup 2+} and the triplet ligand field excited states of Rh(NH{sub 3}){sub 5}{sup 3+}.« less
  • The cyanide (C{sup 15}N{sup {minus}}) complex of Pseudomonas putida cytochrome P-450 (P-450{sub cam}) exhibited well-resolved and hyperfine-shifted {sup 15}N NMR resonances arising from the iron-bound C{sup 15}N{sup {minus}} at 423 and 500 ppm in the absence and presence of the substrate, d-camphor, respectively. The values were smaller than those for cyanide complexes of myoglobin and hemoglobin ({approx} 1000 ppm) but fell into the same range as those for the cyanide complexes of peroxidases ({approx} 500 ppm). The {sup 15}N shift values of P-450{sub cam} were not incompatible with the existence of anionic ligand, such as cysteinyl thiolate anion, at themore » fifth coordination site of heme iron. The difference in the {sup 15}N chemical shift values between camphor-free and bound enzymes was inferred by the increase in the steric constraint to the Fe-C-N bond upon substrate binding.« less
  • The precipitation of {alpha}{double_prime} iron nitride in FeN martensite (containing about 5.9 N/100 Fe) is studied as a function of tempering time successively at 333 and 373 K by means of X-ray diffractometry (XRD). On the basis of peak (=lattice parameter) shifts and intensity changes of main and superstructure reflections, it is concluded that, during tempering, the structure of the formed {alpha}{double_prime} precipitates changes. At 333 K, initially stoichiometric Fe{sub 16}N{sub 2} is formed and, with further tempering, structural vacancies are introduced, i.e., Fe{sub 16}N{sub 2{minus}x} is formed. At 373 K, the vacancies are partially filled. The change of themore » {alpha}{double_prime} structure at 333 K is caused by the change of the matrix from martensite to ferrite, i.e., the misfit between the {alpha}{double_prime} and the matrix is initially relatively small and then increases. By allowing nitrogen-deficient {alpha}{double_prime}, the increase of the misfit can be diminished at the expense of some increase of the volume of {alpha}{double_prime}. Gibbs free energy calculations (at 333 K), in which differences in the misfit energy are decisive, indeed show that, in a martensite matrix, Fe{sub 16}N{sub 2} is favored, whereas, in a ferrite matrix, Fe{sub 16}N{sub 2{minus}x} is favored. Further, in this article, methods are presented to calculate structure factors for nitrogen-deficient {alpha}{double_prime} and to obtain, from measured (=strained) lattice parameters, strain-free {alpha}{double_prime} lattice parameters from which the composition can be deduced.« less
  • Two species of monodisperse nanocrystals (NCs) can self-assemble into a variety of complex 2D and 3D periodic structures, or binary NC superlattice (BNSL) films, based on the relative number and size of the NCs. BNSL films offer great promise for both fundamental scientific studies and optoelectronic applications; however, the utility of as-assembled structures has been limited by the insulating ligands that originate from the synthesis of NCs. Here we report the application of an in situ ligand exchange strategy at a liquid–air interface to replace the long synthesis ligands with short ligands while preserving the long-range order of BNSL films.more » This approach is demonstrated for BNSL structures consisting of PbSe NCs of different size combinations and ligands of interest for photovoltaic devices, infrared detectors, and light-emitting diodes. To confirm enhanced coupling introduced by ligand exchange, we show ultrafast (~1 ps) directional carrier transfer across the type-I heterojunction formed by NCs of different sizes within ligand-exchanged BNSL films. In conclusion, this approach shows the potential promise of functional BNSL films, where the local and long-range energy landscape and electronic coupling can be adjusted by tuning NC composition, size, and interparticle spacing.« less