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Title: Vibrational spectra and structure of {open_quotes}staircase{close_quotes} carbonyl {pi}-complexes of transition metals 1. Electronic effects

Abstract

FTIR spectra have been studied for {open_quotes}staircase{close_quotes} cyclopentadienyl complexes comprising two or three metal carbonyl fragments bound by the metal-carbon bond Cp(CO){sub 2}Fe-CpmMn(CO){sub 3}, Cp(CO){sub 2}Fe-CpmFe(CO){sub 2}CH{sub 2}Ph, Cp(CO){sub 2}Fe-Cpm(CO){sub 2}Fe-CpmMn(CO){sub 3}, Cp(CO){sub 2}Mo-Cpm(CO){sub 2}Fe-CpmMn(CO){sub 3}, Cp(CO){sub 3}W-Cpm(CO){sub 2}Fe-CpmMn(CO){sub 3}, Cp(CO){sub 2}Fe-Cpm(CO){sub 2}Fe-BmCr(CO){sub 3}, Cr(CO){sub 3}Bm-CpmFe(CO){sub 2}CH{sub 2}Ph, where Cp = {eta}{sup 5}-C{sub 5}H{sub 5}, Cpm = {eta}{sup 1}: {eta}{sup 5}-C{sub 5}H{sub 4}, Bm = {eta}{sup 1}:{eta}{sup 6}-C{sub 6}H{sub 5}, as well as mononuclear model complexes Cp(CO){sub 2}Fe(CH){sub 2}Ph, CpMn(CO){sub 3}, and ({eta}{sup 6}-C{sub 6}H{sub 6})Cr(CO){sub 3}. The spectra were interpreted on the basis of the local symmetry of each metal carbonyl center. The positions of vCOs are determined by the mutual electronic effect of each center. CpmM(CO){sub n} groups are strong electron acceptors and cause an increase in vCOs of adjacent M(CO){sub n} groups. Cp(CO){sub n}M groups, being electron donors, cause a decrease in the frequencies of neighboring groups. In trinuclear complexes, the frequencies of the central Fe(CO){sub 2} group are not changed much due to the compensation of donor and acceptor influences of two neighboring substituents.

Authors:
; ; ;  [1];  [2]
  1. A.N. Nesmeyanov Institute of Organoelement Compounds, Moscow (Russian Federation)
  2. Institute of High Temperature Thermodynamics, Rome (Italy)
Publication Date:
OSTI Identifier:
75660
Resource Type:
Journal Article
Journal Name:
Russian Chemical Bulletin
Additional Journal Information:
Journal Volume: 43; Journal Issue: 11; Other Information: PBD: May 1995; TN: Translated from Izvestiya Akademii Nauk. Seriya Khimicheskaya; No. 11, 1948-1951(Nov 1994)
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; IRON COMPLEXES; VIBRATIONAL STATES; MANGANESE COMPLEXES; ORGANOMETALLIC COMPOUNDS; TUNGSTEN COMPLEXES; CHROMIUM COMPLEXES; MOLYBDENUM COMPLEXES; CARBONYLS; MOLECULAR STRUCTURE; ELECTRONIC STRUCTURE; ABSORPTION SPECTROSCOPY

Citation Formats

Ezernitskaya, M G, Lokshin, B V, Orlova, T Yu, Setkina, V N, and Cesaro, S N. Vibrational spectra and structure of {open_quotes}staircase{close_quotes} carbonyl {pi}-complexes of transition metals 1. Electronic effects. United States: N. p., 1995. Web.
Ezernitskaya, M G, Lokshin, B V, Orlova, T Yu, Setkina, V N, & Cesaro, S N. Vibrational spectra and structure of {open_quotes}staircase{close_quotes} carbonyl {pi}-complexes of transition metals 1. Electronic effects. United States.
Ezernitskaya, M G, Lokshin, B V, Orlova, T Yu, Setkina, V N, and Cesaro, S N. 1995. "Vibrational spectra and structure of {open_quotes}staircase{close_quotes} carbonyl {pi}-complexes of transition metals 1. Electronic effects". United States.
@article{osti_75660,
title = {Vibrational spectra and structure of {open_quotes}staircase{close_quotes} carbonyl {pi}-complexes of transition metals 1. Electronic effects},
author = {Ezernitskaya, M G and Lokshin, B V and Orlova, T Yu and Setkina, V N and Cesaro, S N},
abstractNote = {FTIR spectra have been studied for {open_quotes}staircase{close_quotes} cyclopentadienyl complexes comprising two or three metal carbonyl fragments bound by the metal-carbon bond Cp(CO){sub 2}Fe-CpmMn(CO){sub 3}, Cp(CO){sub 2}Fe-CpmFe(CO){sub 2}CH{sub 2}Ph, Cp(CO){sub 2}Fe-Cpm(CO){sub 2}Fe-CpmMn(CO){sub 3}, Cp(CO){sub 2}Mo-Cpm(CO){sub 2}Fe-CpmMn(CO){sub 3}, Cp(CO){sub 3}W-Cpm(CO){sub 2}Fe-CpmMn(CO){sub 3}, Cp(CO){sub 2}Fe-Cpm(CO){sub 2}Fe-BmCr(CO){sub 3}, Cr(CO){sub 3}Bm-CpmFe(CO){sub 2}CH{sub 2}Ph, where Cp = {eta}{sup 5}-C{sub 5}H{sub 5}, Cpm = {eta}{sup 1}: {eta}{sup 5}-C{sub 5}H{sub 4}, Bm = {eta}{sup 1}:{eta}{sup 6}-C{sub 6}H{sub 5}, as well as mononuclear model complexes Cp(CO){sub 2}Fe(CH){sub 2}Ph, CpMn(CO){sub 3}, and ({eta}{sup 6}-C{sub 6}H{sub 6})Cr(CO){sub 3}. The spectra were interpreted on the basis of the local symmetry of each metal carbonyl center. The positions of vCOs are determined by the mutual electronic effect of each center. CpmM(CO){sub n} groups are strong electron acceptors and cause an increase in vCOs of adjacent M(CO){sub n} groups. Cp(CO){sub n}M groups, being electron donors, cause a decrease in the frequencies of neighboring groups. In trinuclear complexes, the frequencies of the central Fe(CO){sub 2} group are not changed much due to the compensation of donor and acceptor influences of two neighboring substituents.},
doi = {},
url = {https://www.osti.gov/biblio/75660}, journal = {Russian Chemical Bulletin},
number = 11,
volume = 43,
place = {United States},
year = {Mon May 01 00:00:00 EDT 1995},
month = {Mon May 01 00:00:00 EDT 1995}
}