The strongest CO binding and the highest C-O stretching frequency

Ranajit Saha; Sudip Pan; Gernot Frenking; Pratim K. Chattaraj; Gabriel Merino

doi:10.1039/c6cp06824c

The strongest CO binding and the highest C-O stretching frequency

Ranajit Saha, Sudip Pan, Gernot Frenking, Pratim K. Chattaraj, Gabriel Merino

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17 Scopus citations

Abstract

A coupled-cluster study is performed on CO bound BeY complexes (Y = O, CO₃, SO₄, NH, NCN, and NBO) to understand the effect of attached ligands (Y) on the CO binding ability and C-O stretching frequency (ν_CO). Herein, we report that BeNCN has the highest CO binding ability (via both C- and O-side binding) among the studied neutral Be-based clusters, whereas OCBeSO₄ has the highest ν_CO among the neutral carbonyls. The nature and extent of shift in ν_CO compared to free CO are explained in terms of change in polarization in the bonding orbitals of CO and relative contribution from OC→BeY or CO→BeY σ-donation, and OC←BeY or CO←BeY π-back-donation. The largest blue-shift in OCBeSO₄ and the largest red-shift in COBeNH are consequences of the smallest OC←BeSO₄ π-back-donation and the largest CO←BeNH π-back-donation, respectively.

Original language	English
Pages (from-to)	2286-2293
Number of pages	8
Journal	Physical Chemistry Chemical Physics
Volume	19
Issue number	3
DOIs	https://doi.org/10.1039/c6cp06824c
State	Published - 2017
Externally published	Yes

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title = "The strongest CO binding and the highest C-O stretching frequency",

abstract = "A coupled-cluster study is performed on CO bound BeY complexes (Y = O, CO3, SO4, NH, NCN, and NBO) to understand the effect of attached ligands (Y) on the CO binding ability and C-O stretching frequency (νCO). Herein, we report that BeNCN has the highest CO binding ability (via both C- and O-side binding) among the studied neutral Be-based clusters, whereas OCBeSO4 has the highest νCO among the neutral carbonyls. The nature and extent of shift in νCO compared to free CO are explained in terms of change in polarization in the bonding orbitals of CO and relative contribution from OC→BeY or CO→BeY σ-donation, and OC←BeY or CO←BeY π-back-donation. The largest blue-shift in OCBeSO4 and the largest red-shift in COBeNH are consequences of the smallest OC←BeSO4 π-back-donation and the largest CO←BeNH π-back-donation, respectively.",

author = "Ranajit Saha and Sudip Pan and Gernot Frenking and Chattaraj, {Pratim K.} and Gabriel Merino",

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doi = "10.1039/c6cp06824c",

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T1 - The strongest CO binding and the highest C-O stretching frequency

AU - Saha, Ranajit

AU - Pan, Sudip

AU - Frenking, Gernot

AU - Chattaraj, Pratim K.

AU - Merino, Gabriel

N1 - Publisher Copyright: © the Owner Societies 2017.

PY - 2017

Y1 - 2017

N2 - A coupled-cluster study is performed on CO bound BeY complexes (Y = O, CO3, SO4, NH, NCN, and NBO) to understand the effect of attached ligands (Y) on the CO binding ability and C-O stretching frequency (νCO). Herein, we report that BeNCN has the highest CO binding ability (via both C- and O-side binding) among the studied neutral Be-based clusters, whereas OCBeSO4 has the highest νCO among the neutral carbonyls. The nature and extent of shift in νCO compared to free CO are explained in terms of change in polarization in the bonding orbitals of CO and relative contribution from OC→BeY or CO→BeY σ-donation, and OC←BeY or CO←BeY π-back-donation. The largest blue-shift in OCBeSO4 and the largest red-shift in COBeNH are consequences of the smallest OC←BeSO4 π-back-donation and the largest CO←BeNH π-back-donation, respectively.

AB - A coupled-cluster study is performed on CO bound BeY complexes (Y = O, CO3, SO4, NH, NCN, and NBO) to understand the effect of attached ligands (Y) on the CO binding ability and C-O stretching frequency (νCO). Herein, we report that BeNCN has the highest CO binding ability (via both C- and O-side binding) among the studied neutral Be-based clusters, whereas OCBeSO4 has the highest νCO among the neutral carbonyls. The nature and extent of shift in νCO compared to free CO are explained in terms of change in polarization in the bonding orbitals of CO and relative contribution from OC→BeY or CO→BeY σ-donation, and OC←BeY or CO←BeY π-back-donation. The largest blue-shift in OCBeSO4 and the largest red-shift in COBeNH are consequences of the smallest OC←BeSO4 π-back-donation and the largest CO←BeNH π-back-donation, respectively.

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DO - 10.1039/c6cp06824c

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SN - 1463-9076

VL - 19

SP - 2286

EP - 2293

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

IS - 3

ER -

The strongest CO binding and the highest C-O stretching frequency

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