Influence of Substituents on the Electronic Structure of Mono- and Bis(phosphido) Thorium(IV) Complexes

Pokpong Rungthanaphatsophon; Thomas J. Duignan; Alexander J. Myers; Sean P. Vilanova; Charles L. Barnes; Jochen Autschbach; Enrique R. Batista; Ping Yang; Justin R. Walensky

doi:10.1021/acs.inorgchem.8b00922

Influence of Substituents on the Electronic Structure of Mono- and Bis(phosphido) Thorium(IV) Complexes

Pokpong Rungthanaphatsophon
, Thomas J. Duignan
, Alexander J. Myers
, Sean P. Vilanova
, Charles L. Barnes
, Jochen Autschbach
, Enrique R. Batista
, Ping Yang
, Justin R. Walensky

Chemistry

University of Missouri
Los Alamos National Laboratory Theoretical Division
SUNY Buffalo

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

14 Scopus citations

Abstract

A series of metallocene thorium complexes with mono- and bis(phosphido) ligands have been investigated with varying hues: (C₅Me₅)₂Th(Cl)[P(Mes)₂] (Mes = mesityl = 2,4,6-(CH₃)₃C₆H₂; dark red-purple), (C₅Me₅)₂Th[P(Mes)(CH₃)]₂ (dark red-purple), (C₅Me₅)₂Th(CH₃)[P(Mes)₂] (dark red-purple), (C₅Me₅)₂Th(CH₃)[P(Mes)(SiMe₃)] (orange), (C₅Me₅)₂Th(Cl)[P(Mes)(SiMe₃)] (orange), (C₅Me₅)₂Th[P(Mes)(SiMe₃)]₂ (orange), and (C₅Me₅)₂Th[PH(Mes)]₂ (pale yellow). While all of these complexes bear a mesityl group on phosphorus, the electronic structure observed differs depending on the other substituent (mesityl, methyl, trimethylsilyl, or hydrogen). This sparked an investigation of the electronic structure of these complexes using ³¹P NMR and electronic absorption spectroscopy in concert with time-dependent density functional theory calculations.

Original language	English
Pages (from-to)	7270-7278
Number of pages	9
Journal	Inorganic Chemistry
Volume	57
Issue number	12
DOIs	https://doi.org/10.1021/acs.inorgchem.8b00922
State	Published - Jun 18 2018

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10.1021/acs.inorgchem.8b00922

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title = "Influence of Substituents on the Electronic Structure of Mono- and Bis(phosphido) Thorium(IV) Complexes",

abstract = "A series of metallocene thorium complexes with mono- and bis(phosphido) ligands have been investigated with varying hues: (C5Me5)2Th(Cl)[P(Mes)2] (Mes = mesityl = 2,4,6-(CH3)3C6H2; dark red-purple), (C5Me5)2Th[P(Mes)(CH3)]2 (dark red-purple), (C5Me5)2Th(CH3)[P(Mes)2] (dark red-purple), (C5Me5)2Th(CH3)[P(Mes)(SiMe3)] (orange), (C5Me5)2Th(Cl)[P(Mes)(SiMe3)] (orange), (C5Me5)2Th[P(Mes)(SiMe3)]2 (orange), and (C5Me5)2Th[PH(Mes)]2 (pale yellow). While all of these complexes bear a mesityl group on phosphorus, the electronic structure observed differs depending on the other substituent (mesityl, methyl, trimethylsilyl, or hydrogen). This sparked an investigation of the electronic structure of these complexes using 31P NMR and electronic absorption spectroscopy in concert with time-dependent density functional theory calculations.",

author = "Pokpong Rungthanaphatsophon and Duignan, \{Thomas J.\} and Myers, \{Alexander J.\} and Vilanova, \{Sean P.\} and Barnes, \{Charles L.\} and Jochen Autschbach and Batista, \{Enrique R.\} and Ping Yang and Walensky, \{Justin R.\}",

note = "Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

month = jun,

day = "18",

doi = "10.1021/acs.inorgchem.8b00922",

language = "English",

volume = "57",

pages = "7270--7278",

journal = "Inorganic Chemistry",

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T1 - Influence of Substituents on the Electronic Structure of Mono- and Bis(phosphido) Thorium(IV) Complexes

AU - Rungthanaphatsophon, Pokpong

AU - Duignan, Thomas J.

AU - Myers, Alexander J.

AU - Vilanova, Sean P.

AU - Barnes, Charles L.

AU - Autschbach, Jochen

AU - Batista, Enrique R.

AU - Yang, Ping

AU - Walensky, Justin R.

PY - 2018/6/18

Y1 - 2018/6/18

N2 - A series of metallocene thorium complexes with mono- and bis(phosphido) ligands have been investigated with varying hues: (C5Me5)2Th(Cl)[P(Mes)2] (Mes = mesityl = 2,4,6-(CH3)3C6H2; dark red-purple), (C5Me5)2Th[P(Mes)(CH3)]2 (dark red-purple), (C5Me5)2Th(CH3)[P(Mes)2] (dark red-purple), (C5Me5)2Th(CH3)[P(Mes)(SiMe3)] (orange), (C5Me5)2Th(Cl)[P(Mes)(SiMe3)] (orange), (C5Me5)2Th[P(Mes)(SiMe3)]2 (orange), and (C5Me5)2Th[PH(Mes)]2 (pale yellow). While all of these complexes bear a mesityl group on phosphorus, the electronic structure observed differs depending on the other substituent (mesityl, methyl, trimethylsilyl, or hydrogen). This sparked an investigation of the electronic structure of these complexes using 31P NMR and electronic absorption spectroscopy in concert with time-dependent density functional theory calculations.

AB - A series of metallocene thorium complexes with mono- and bis(phosphido) ligands have been investigated with varying hues: (C5Me5)2Th(Cl)[P(Mes)2] (Mes = mesityl = 2,4,6-(CH3)3C6H2; dark red-purple), (C5Me5)2Th[P(Mes)(CH3)]2 (dark red-purple), (C5Me5)2Th(CH3)[P(Mes)2] (dark red-purple), (C5Me5)2Th(CH3)[P(Mes)(SiMe3)] (orange), (C5Me5)2Th(Cl)[P(Mes)(SiMe3)] (orange), (C5Me5)2Th[P(Mes)(SiMe3)]2 (orange), and (C5Me5)2Th[PH(Mes)]2 (pale yellow). While all of these complexes bear a mesityl group on phosphorus, the electronic structure observed differs depending on the other substituent (mesityl, methyl, trimethylsilyl, or hydrogen). This sparked an investigation of the electronic structure of these complexes using 31P NMR and electronic absorption spectroscopy in concert with time-dependent density functional theory calculations.

UR - https://www.scopus.com/pages/publications/85048679759

U2 - 10.1021/acs.inorgchem.8b00922

DO - 10.1021/acs.inorgchem.8b00922

M3 - Article

C2 - 29855186

AN - SCOPUS:85048679759

SN - 0020-1669

VL - 57

SP - 7270

EP - 7278

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 12

ER -

Influence of Substituents on the Electronic Structure of Mono- and Bis(phosphido) Thorium(IV) Complexes

Abstract

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