Computational Insight into Rh-103 Chemical Shift-Structure Correlations in Rhodium Bis(phosphine) Complexes

Manuel A. Ortuno; Ludovic Castro; Michael Buehl

doi:10.1021/om400774y

Computational Insight into Rh-103 Chemical Shift-Structure Correlations in Rhodium Bis(phosphine) Complexes

Manuel A. Ortuno, Ludovic Castro, Michael Buehl^*

^*Corresponding author for this work

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

Abstract

¹⁰³RhNMR chemical shifts have been computed at the GIAO-B3LYP level of density functional theory (DFT) for a number of [Rh(COD)(P∩P)]⁺ complexes [COD = 1,5-cyclooctadiene, P∩P = chelating bis(phosphine) including
bis(dimethylphosphino)ethane (dmpe), bis(diphenylphosphino)ethane (dmpe),
MeDUPHOS, DIOP, BINAP, and others]. Structures have been optimized using PBE0
and M06 functionals in the gas phase, in a continuum modeling the solvent, and
with [PF₆]⁻counteranion included explicitly. Observed trends in δ(¹⁰³Rh)
are well reproduced for pristine PBE0-optimized cations in the gas phase or for
ion pairs optimized in a continuum with M06. While there is no overall trend
between computed δ(¹⁰³Rh) values and complex stabilities (evaluated through isodesmic ligand exchange reactions), there is a linear relationship between the ¹⁰³Rh chemical shifts and the mean Rh–P bond distances. This relationship appears to be remarkably general, encompassing various chelating ring sizes and
substituents at P, including remote electron-donating and -withdrawing
substituents that are characterized through their Hammett constants. The
combination of ¹⁰³Rh NMR and DFT computations emerges as a useful tool for structure elucidation of Rh–phosphine complexes.

Original language	English
Pages (from-to)	6437-6444
Number of pages	8
Journal	Organometallics
Volume	32
Issue number	21
Early online date	4 Oct 2013
DOIs	https://doi.org/10.1021/om400774y
Publication status	Published - 11 Nov 2013

Keywords

Density-functional theory
Transition-metal-complexes
Molecular orbital methods
NMR spectroscopy
Basis sets
Organometallic complexes
Noncovalent interactions
Diolefin complexes
Shielding tensors
Olefin complexes

Access to Document

10.1021/om400774y

pubManuelRh_revised
Copyright 2013, American Chemical Society. This document is the unedited author's version of a Submitted Work that was subsequently accepted for publication in Organometallics after peer review. To access the final edited and published work, see http://pubs.acs.org/doi/abs/10.1021/om400774y
Accepted author manuscript, 741 KB

Cite this

@article{20a69c481c564d8d9ac8e86757e7692f,

title = "Computational Insight into Rh-103 Chemical Shift-Structure Correlations in Rhodium Bis(phosphine) Complexes",

abstract = "103RhNMR chemical shifts have been computed at the GIAO-B3LYP level of density functional theory (DFT) for a number of [Rh(COD)(P∩P)]+ complexes [COD = 1,5-cyclooctadiene, P∩P = chelating bis(phosphine) including bis(dimethylphosphino)ethane (dmpe), bis(diphenylphosphino)ethane (dmpe), MeDUPHOS, DIOP, BINAP, and others]. Structures have been optimized using PBE0 and M06 functionals in the gas phase, in a continuum modeling the solvent, and with [PF6]− counteranion included explicitly. Observed trends in δ(103Rh) are well reproduced for pristine PBE0-optimized cations in the gas phase or for ion pairs optimized in a continuum with M06. While there is no overall trend between computed δ(103Rh) values and complex stabilities (evaluated through isodesmic ligand exchange reactions), there is a linear relationship between the 103Rh chemical shifts and the mean Rh–P bond distances. This relationship appears to be remarkably general, encompassing various chelating ring sizes and substituents at P, including remote electron-donating and -withdrawing substituents that are characterized through their Hammett constants. The combination of 103Rh NMR and DFT computations emerges as a useful tool for structure elucidation of Rh–phosphine complexes.",

keywords = "Density-functional theory, Transition-metal-complexes, Molecular orbital methods, NMR spectroscopy, Basis sets, Organometallic complexes, Noncovalent interactions, Diolefin complexes, Shielding tensors, Olefin complexes ",

author = "Ortuno, {Manuel A.} and Ludovic Castro and Michael Buehl",

year = "2013",

month = nov,

day = "11",

doi = "10.1021/om400774y",

language = "English",

volume = "32",

pages = "6437--6444",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society (ACS)",

number = "21",

}

TY - JOUR

T1 - Computational Insight into Rh-103 Chemical Shift-Structure Correlations in Rhodium Bis(phosphine) Complexes

AU - Ortuno, Manuel A.

AU - Castro, Ludovic

AU - Buehl, Michael

PY - 2013/11/11

Y1 - 2013/11/11

N2 - 103RhNMR chemical shifts have been computed at the GIAO-B3LYP level of density functional theory (DFT) for a number of [Rh(COD)(P∩P)]+ complexes [COD = 1,5-cyclooctadiene, P∩P = chelating bis(phosphine) including bis(dimethylphosphino)ethane (dmpe), bis(diphenylphosphino)ethane (dmpe), MeDUPHOS, DIOP, BINAP, and others]. Structures have been optimized using PBE0 and M06 functionals in the gas phase, in a continuum modeling the solvent, and with [PF6]− counteranion included explicitly. Observed trends in δ(103Rh) are well reproduced for pristine PBE0-optimized cations in the gas phase or for ion pairs optimized in a continuum with M06. While there is no overall trend between computed δ(103Rh) values and complex stabilities (evaluated through isodesmic ligand exchange reactions), there is a linear relationship between the 103Rh chemical shifts and the mean Rh–P bond distances. This relationship appears to be remarkably general, encompassing various chelating ring sizes and substituents at P, including remote electron-donating and -withdrawing substituents that are characterized through their Hammett constants. The combination of 103Rh NMR and DFT computations emerges as a useful tool for structure elucidation of Rh–phosphine complexes.

AB - 103RhNMR chemical shifts have been computed at the GIAO-B3LYP level of density functional theory (DFT) for a number of [Rh(COD)(P∩P)]+ complexes [COD = 1,5-cyclooctadiene, P∩P = chelating bis(phosphine) including bis(dimethylphosphino)ethane (dmpe), bis(diphenylphosphino)ethane (dmpe), MeDUPHOS, DIOP, BINAP, and others]. Structures have been optimized using PBE0 and M06 functionals in the gas phase, in a continuum modeling the solvent, and with [PF6]− counteranion included explicitly. Observed trends in δ(103Rh) are well reproduced for pristine PBE0-optimized cations in the gas phase or for ion pairs optimized in a continuum with M06. While there is no overall trend between computed δ(103Rh) values and complex stabilities (evaluated through isodesmic ligand exchange reactions), there is a linear relationship between the 103Rh chemical shifts and the mean Rh–P bond distances. This relationship appears to be remarkably general, encompassing various chelating ring sizes and substituents at P, including remote electron-donating and -withdrawing substituents that are characterized through their Hammett constants. The combination of 103Rh NMR and DFT computations emerges as a useful tool for structure elucidation of Rh–phosphine complexes.

KW - Density-functional theory

KW - Transition-metal-complexes

KW - Molecular orbital methods

KW - NMR spectroscopy

KW - Basis sets

KW - Organometallic complexes

KW - Noncovalent interactions

KW - Diolefin complexes

KW - Shielding tensors

KW - Olefin complexes

U2 - 10.1021/om400774y

DO - 10.1021/om400774y

M3 - Article

SN - 0276-7333

VL - 32

SP - 6437

EP - 6444

JO - Organometallics

JF - Organometallics

IS - 21

ER -

Computational Insight into Rh-103 Chemical Shift-Structure Correlations in Rhodium Bis(phosphine) Complexes

Abstract

Keywords

Access to Document

Fingerprint

Cite this