Into the Role of Unsaturated Trinuclear Metal Carbonyls in the Formation of [M3(2,3-bpp)(CO)10] with M=Ru, Os: A DFT Stability Analysis and Electronic Structure

Katherine Paredes-Gil; Esperanza Galarza; Jose Y. Aguilar-Hurtado; Eduardo Solís-Céspedes; Dayán Páez-Hernández

doi:10.1007/s10876-022-02389-1

Into the Role of Unsaturated Trinuclear Metal Carbonyls in the Formation of [M₃(2,3-bpp)(CO)₁₀] with M=Ru, Os: A DFT Stability Analysis and Electronic Structure

Katherine Paredes-Gil, Esperanza Galarza, Jose Y. Aguilar-Hurtado, Eduardo Solís-Céspedes, Dayán Páez-Hernández

Research output: Contribution to journal › Article › peer-review

Abstract

The metal carbonyl clusters have been recognized as one of the most successful organometallic complexes with extensive catalytic applications. In this paper, we carried out a DFT study of the stability, electronic structure and thermodynamic properties of the intermediates [M₃(CO)₁₁] and [M₃(CO)₁₀] in the synthesis of [M₃(2,3-bpp)(CO)₁₀] (M=Ru and Os). CO binding energy analysis revealed that [M₃(CO)₁₀(μ-CO)], [Ru₃(CO)₈(μ-CO)₂] and [Os₃(CO)₆(μ₃-CO)₂(μ-CO)₂] are the most stables compounds due to the presence of bridge carbonyls which favor a covalent interaction. Sigma donation from the carbonyl to metal d orbital is the most significant contribution. Moreover, spectroscopic and computational studies indicated that [Ru₃(2,3-bpp)(CO)₁₀] is in good agreement with the analogues osmium complex. Regarding the pathway associated to the formation of [M₃(2,3-bpp)(CO)₁₀] we have found that the determinant step is the dissociation of a second CO axial into [M₃(CO)₁₀(μ-CO)]. Thus, unsaturated metal carbonyl intermediates exert a thermodynamic and kinetically control as consequence of the orbital reorganization.

Original language	English
Journal	Journal of Cluster Science
DOIs	https://doi.org/10.1007/s10876-022-02389-1
Publication status	Accepted/In press - 2022

Keywords

Carbonyl clusters
Density functional theory
Energy decomposition analysis

ASJC Scopus subject areas

General Chemistry
Biochemistry
General Materials Science
Condensed Matter Physics

Access to Document

10.1007/s10876-022-02389-1

Cite this

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title = "Into the Role of Unsaturated Trinuclear Metal Carbonyls in the Formation of [M3(2,3-bpp)(CO)10] with M=Ru, Os: A DFT Stability Analysis and Electronic Structure",

abstract = "The metal carbonyl clusters have been recognized as one of the most successful organometallic complexes with extensive catalytic applications. In this paper, we carried out a DFT study of the stability, electronic structure and thermodynamic properties of the intermediates [M3(CO)11] and [M3(CO)10] in the synthesis of [M3(2,3-bpp)(CO)10] (M=Ru and Os). CO binding energy analysis revealed that [M3(CO)10(μ-CO)], [Ru3(CO)8(μ-CO)2] and [Os3(CO)6(μ3-CO)2(μ-CO)2] are the most stables compounds due to the presence of bridge carbonyls which favor a covalent interaction. Sigma donation from the carbonyl to metal d orbital is the most significant contribution. Moreover, spectroscopic and computational studies indicated that [Ru3(2,3-bpp)(CO)10] is in good agreement with the analogues osmium complex. Regarding the pathway associated to the formation of [M3(2,3-bpp)(CO)10] we have found that the determinant step is the dissociation of a second CO axial into [M3(CO)10(μ-CO)]. Thus, unsaturated metal carbonyl intermediates exert a thermodynamic and kinetically control as consequence of the orbital reorganization.",

keywords = "Carbonyl clusters, Density functional theory, Energy decomposition analysis",

author = "Katherine Paredes-Gil and Esperanza Galarza and Aguilar-Hurtado, {Jose Y.} and Eduardo Sol{\'i}s-C{\'e}spedes and Day{\'a}n P{\'a}ez-Hern{\'a}ndez",

note = "Publisher Copyright: {\textcopyright} 2022, The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.",

year = "2022",

doi = "10.1007/s10876-022-02389-1",

language = "English",

journal = "Journal of Cluster Science",

issn = "1040-7278",

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T1 - Into the Role of Unsaturated Trinuclear Metal Carbonyls in the Formation of [M3(2,3-bpp)(CO)10] with M=Ru, Os

T2 - A DFT Stability Analysis and Electronic Structure

AU - Paredes-Gil, Katherine

AU - Galarza, Esperanza

AU - Aguilar-Hurtado, Jose Y.

AU - Solís-Céspedes, Eduardo

AU - Páez-Hernández, Dayán

PY - 2022

Y1 - 2022

N2 - The metal carbonyl clusters have been recognized as one of the most successful organometallic complexes with extensive catalytic applications. In this paper, we carried out a DFT study of the stability, electronic structure and thermodynamic properties of the intermediates [M3(CO)11] and [M3(CO)10] in the synthesis of [M3(2,3-bpp)(CO)10] (M=Ru and Os). CO binding energy analysis revealed that [M3(CO)10(μ-CO)], [Ru3(CO)8(μ-CO)2] and [Os3(CO)6(μ3-CO)2(μ-CO)2] are the most stables compounds due to the presence of bridge carbonyls which favor a covalent interaction. Sigma donation from the carbonyl to metal d orbital is the most significant contribution. Moreover, spectroscopic and computational studies indicated that [Ru3(2,3-bpp)(CO)10] is in good agreement with the analogues osmium complex. Regarding the pathway associated to the formation of [M3(2,3-bpp)(CO)10] we have found that the determinant step is the dissociation of a second CO axial into [M3(CO)10(μ-CO)]. Thus, unsaturated metal carbonyl intermediates exert a thermodynamic and kinetically control as consequence of the orbital reorganization.

AB - The metal carbonyl clusters have been recognized as one of the most successful organometallic complexes with extensive catalytic applications. In this paper, we carried out a DFT study of the stability, electronic structure and thermodynamic properties of the intermediates [M3(CO)11] and [M3(CO)10] in the synthesis of [M3(2,3-bpp)(CO)10] (M=Ru and Os). CO binding energy analysis revealed that [M3(CO)10(μ-CO)], [Ru3(CO)8(μ-CO)2] and [Os3(CO)6(μ3-CO)2(μ-CO)2] are the most stables compounds due to the presence of bridge carbonyls which favor a covalent interaction. Sigma donation from the carbonyl to metal d orbital is the most significant contribution. Moreover, spectroscopic and computational studies indicated that [Ru3(2,3-bpp)(CO)10] is in good agreement with the analogues osmium complex. Regarding the pathway associated to the formation of [M3(2,3-bpp)(CO)10] we have found that the determinant step is the dissociation of a second CO axial into [M3(CO)10(μ-CO)]. Thus, unsaturated metal carbonyl intermediates exert a thermodynamic and kinetically control as consequence of the orbital reorganization.

KW - Carbonyl clusters

KW - Density functional theory

KW - Energy decomposition analysis

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