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Title: An attractive cis-effect of hydride on neighbor ligands: Experimental and theoretical studies on the structure and intramolecular rearrangements of Fe(H) sub 2 (. eta. sup 2 -H sub 2 )(PEtPh sub 2 ) sub 3

Abstract

The compound of formula FeH{sub 4}(PEtPh{sub 2}){sub 3} has been established by neutron diffraction to possess the structure and linkage cis,mer-Fe(H{sub 2})(PEtPh{sub 2}){sub 3}, and thus be generally similar in structure to cis,mer-Fe(H){sub 2}(N{sub 2})(PEtPh{sub 2}){sub 3}, whose structure has been determined by X-ray diffraction. The Fe-hydride distances in Fe(H){sub 2}(PEtPh{sub 2}){sub 3} are 1.538 (7) {angstrom} (trans to H{sub 2}) and 1.514 (6) {angstrom} (trans to PEtPh{sub 2}), and the Fe-H (of H{sub 2}) distances are 1.607 (8) and 1.576 (9) {angstrom}. The H-H distance in coordinated dihydrogen is 0.821 (10) {angstrom}, but the H-H bond adopts an orientation unique among structurally characterized octahedral H{sub 2} complexes: staggered with respect to the cis Fe-P and Fe-H axes. Vibrational frequencies of the Fe(H){sub 2}(H{sub 2}) substructure have been measured by difference inelastic neutron scattering spectroscopy. Neutron scattering also reveals the low-frequency rotational tunneling splitting, allowing estimation of the height of the torsional barrier for coordinated H{sub 2} rotating about its midpoint ({approximately}1 kcal/mol).

Authors:
; ;  [1]; ; ; ;  [2]; ;  [3];  [4]
  1. Indiana Univ., Bloomington (USA)
  2. Los Alamos National Laboratory, NM (USA)
  3. Centre de Paris-Sud, Orsay (France)
  4. Brookhaven National Laboratory, Upton, NY (USA)
Publication Date:
OSTI Identifier:
6880093
DOE Contract Number:  
AC02-76CH00016
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society; (USA)
Additional Journal Information:
Journal Volume: 112:12; Journal ID: ISSN 0002-7863
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; HYDRIDES; STRUCTURAL CHEMICAL ANALYSIS; DATA ANALYSIS; EXPERIMENTAL DATA; LIGANDS; MEASURING INSTRUMENTS; MEASURING METHODS; ORGANOMETALLIC COMPOUNDS; VIBRATIONAL STATES; DATA; ENERGY LEVELS; EXCITED STATES; HYDROGEN COMPOUNDS; INFORMATION; NUMERICAL DATA; ORGANIC COMPOUNDS; 400201* - Chemical & Physicochemical Properties

Citation Formats

Van Der Sluys, L S, Huffman, J C, Caulton, K G, Eckert, J, Hall, J H, Kubas, G J, Vergamini, P J, Eisenstein, O, Jackson, S A, and Koetzle, T F. An attractive cis-effect of hydride on neighbor ligands: Experimental and theoretical studies on the structure and intramolecular rearrangements of Fe(H) sub 2 (. eta. sup 2 -H sub 2 )(PEtPh sub 2 ) sub 3. United States: N. p., 1990. Web. doi:10.1021/ja00168a030.
Van Der Sluys, L S, Huffman, J C, Caulton, K G, Eckert, J, Hall, J H, Kubas, G J, Vergamini, P J, Eisenstein, O, Jackson, S A, & Koetzle, T F. An attractive cis-effect of hydride on neighbor ligands: Experimental and theoretical studies on the structure and intramolecular rearrangements of Fe(H) sub 2 (. eta. sup 2 -H sub 2 )(PEtPh sub 2 ) sub 3. United States. https://doi.org/10.1021/ja00168a030
Van Der Sluys, L S, Huffman, J C, Caulton, K G, Eckert, J, Hall, J H, Kubas, G J, Vergamini, P J, Eisenstein, O, Jackson, S A, and Koetzle, T F. 1990. "An attractive cis-effect of hydride on neighbor ligands: Experimental and theoretical studies on the structure and intramolecular rearrangements of Fe(H) sub 2 (. eta. sup 2 -H sub 2 )(PEtPh sub 2 ) sub 3". United States. https://doi.org/10.1021/ja00168a030.
@article{osti_6880093,
title = {An attractive cis-effect of hydride on neighbor ligands: Experimental and theoretical studies on the structure and intramolecular rearrangements of Fe(H) sub 2 (. eta. sup 2 -H sub 2 )(PEtPh sub 2 ) sub 3},
author = {Van Der Sluys, L S and Huffman, J C and Caulton, K G and Eckert, J and Hall, J H and Kubas, G J and Vergamini, P J and Eisenstein, O and Jackson, S A and Koetzle, T F},
abstractNote = {The compound of formula FeH{sub 4}(PEtPh{sub 2}){sub 3} has been established by neutron diffraction to possess the structure and linkage cis,mer-Fe(H{sub 2})(PEtPh{sub 2}){sub 3}, and thus be generally similar in structure to cis,mer-Fe(H){sub 2}(N{sub 2})(PEtPh{sub 2}){sub 3}, whose structure has been determined by X-ray diffraction. The Fe-hydride distances in Fe(H){sub 2}(PEtPh{sub 2}){sub 3} are 1.538 (7) {angstrom} (trans to H{sub 2}) and 1.514 (6) {angstrom} (trans to PEtPh{sub 2}), and the Fe-H (of H{sub 2}) distances are 1.607 (8) and 1.576 (9) {angstrom}. The H-H distance in coordinated dihydrogen is 0.821 (10) {angstrom}, but the H-H bond adopts an orientation unique among structurally characterized octahedral H{sub 2} complexes: staggered with respect to the cis Fe-P and Fe-H axes. Vibrational frequencies of the Fe(H){sub 2}(H{sub 2}) substructure have been measured by difference inelastic neutron scattering spectroscopy. Neutron scattering also reveals the low-frequency rotational tunneling splitting, allowing estimation of the height of the torsional barrier for coordinated H{sub 2} rotating about its midpoint ({approximately}1 kcal/mol).},
doi = {10.1021/ja00168a030},
url = {https://www.osti.gov/biblio/6880093}, journal = {Journal of the American Chemical Society; (USA)},
issn = {0002-7863},
number = ,
volume = 112:12,
place = {United States},
year = {Wed Jun 06 00:00:00 EDT 1990},
month = {Wed Jun 06 00:00:00 EDT 1990}
}