New Pt(II)(dithiolate) Compounds Possessing an Energetically Accessible Diphosphine-Based LUMO: Syntheses, Redox Properties, and Solid-State Structures of PtCl 2(pbpcd), Pt(tdt)(pbpcd), and Pt(tdt)(bpcd)

Sean W. Hunt; Li Yang; Xiaoping Wang; Vladimir Nesterov; Michael G. Richmond

doi:10.1007/s10904-010-9357-6

New Pt(II)(dithiolate) Compounds Possessing an Energetically Accessible Diphosphine-Based LUMO: Syntheses, Redox Properties, and Solid-State Structures of PtCl ₂(pbpcd), Pt(tdt)(pbpcd), and Pt(tdt)(bpcd)

Sean W. Hunt, Li Yang, Xiaoping Wang, Vladimir Nesterov, Michael G. Richmond

Single Crystal Diffraction

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

4 Scopus citations

Abstract

The new ligand 2-(pyren-1-ylidene)-4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (pbpcd) has been synthesized from the Knoevenagel condensation using 1-pyrenecarboxaldehyde with 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd). Displacement of the cod ligand in PtCl ₂(cod) by pbpcd furnishes PtCl ₂(pbpcd) (2) in near quantitative yield. Treatment of 2 with the dipotassium salt of toluene-3,4-dithiol (K ₂tdt) affords the dithiolate compound Pt(tdt)(pbpcd) (3) as a 1:1 mixture of diastereomers. An alternative synthesis of 3 from Pt(tdt)(bpcd) (5) and 1-pyrenecarboxaldehyde also affords 3 in 23% yield. The pbpcd ligand and all new diphosphine-substituted compounds have been isolated and fully characterized in solution by IR and NMR spectroscopies, and the solid-state structures of 2·CH ₂Cl ₂, 3·toluene, and 5·CH ₂Cl ₂ established by X-ray diffraction analyses. The solid-state structure of each product exhibits a square-planar architecture at the metal center. The redox properties of the pbpcd ligand and the tdt-substituted compound 3 have been explored by cyclic and differential-pulse voltammetry, and these data are discussed with respect to extended Hückel MO calculations and the nature of the HOMO and LUMO levels in each compound.

Original language	English
Pages (from-to)	457-467
Number of pages	11
Journal	Journal of Inorganic and Organometallic Polymers and Materials
Volume	20
Issue number	3
DOIs	https://doi.org/10.1007/s10904-010-9357-6
State	Published - 2010

Funding

Acknowledgments Financial support from the Robert A. Welch Foundation (Grant B-1093-MGR) is greatly appreciated, and X. Wang acknowledges the support by the U.S. Department of Energy, Office of Science, under Contract No. DE-AC05-00OR22725 managed by UT Battelle, LLC. Dr. Yongxuan Su is thanked for recording the ESI mass spectra of the platinum compounds 3 and 5 reported herein.

Funders	Funder number
U.S. Department of Energy
Welch Foundation	B-1093-MGR
Office of Science	DE-AC05-00OR22725
UT-Battelle

Keywords

Diphosphine ligand
Dithiolate ligand
MO calculations
Platinum compounds
Redox chemistry
X-ray crystallography

Access to Document

10.1007/s10904-010-9357-6

Cite this

Hunt, S. W., Yang, L., Wang, X., Nesterov, V., & Richmond, M. G. (2010). New Pt(II)(dithiolate) Compounds Possessing an Energetically Accessible Diphosphine-Based LUMO: Syntheses, Redox Properties, and Solid-State Structures of PtCl ₂(pbpcd), Pt(tdt)(pbpcd), and Pt(tdt)(bpcd). Journal of Inorganic and Organometallic Polymers and Materials, 20(3), 457-467. https://doi.org/10.1007/s10904-010-9357-6

@article{6d265999da7f4fe8817586e6318fc481,

title = "New Pt(II)(dithiolate) Compounds Possessing an Energetically Accessible Diphosphine-Based LUMO: Syntheses, Redox Properties, and Solid-State Structures of PtCl 2(pbpcd), Pt(tdt)(pbpcd), and Pt(tdt)(bpcd)",

abstract = "The new ligand 2-(pyren-1-ylidene)-4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (pbpcd) has been synthesized from the Knoevenagel condensation using 1-pyrenecarboxaldehyde with 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd). Displacement of the cod ligand in PtCl 2(cod) by pbpcd furnishes PtCl 2(pbpcd) (2) in near quantitative yield. Treatment of 2 with the dipotassium salt of toluene-3,4-dithiol (K 2tdt) affords the dithiolate compound Pt(tdt)(pbpcd) (3) as a 1:1 mixture of diastereomers. An alternative synthesis of 3 from Pt(tdt)(bpcd) (5) and 1-pyrenecarboxaldehyde also affords 3 in 23% yield. The pbpcd ligand and all new diphosphine-substituted compounds have been isolated and fully characterized in solution by IR and NMR spectroscopies, and the solid-state structures of 2·CH 2Cl 2, 3·toluene, and 5·CH 2Cl 2 established by X-ray diffraction analyses. The solid-state structure of each product exhibits a square-planar architecture at the metal center. The redox properties of the pbpcd ligand and the tdt-substituted compound 3 have been explored by cyclic and differential-pulse voltammetry, and these data are discussed with respect to extended H{\"u}ckel MO calculations and the nature of the HOMO and LUMO levels in each compound.",

keywords = "Diphosphine ligand, Dithiolate ligand, MO calculations, Platinum compounds, Redox chemistry, X-ray crystallography",

author = "Hunt, {Sean W.} and Li Yang and Xiaoping Wang and Vladimir Nesterov and Richmond, {Michael G.}",

year = "2010",

doi = "10.1007/s10904-010-9357-6",

language = "English",

volume = "20",

pages = "457--467",

journal = "Journal of Inorganic and Organometallic Polymers and Materials",

issn = "1574-1443",

publisher = "Springer",

number = "3",

}

Hunt, SW, Yang, L, Wang, X, Nesterov, V & Richmond, MG 2010, 'New Pt(II)(dithiolate) Compounds Possessing an Energetically Accessible Diphosphine-Based LUMO: Syntheses, Redox Properties, and Solid-State Structures of PtCl ₂(pbpcd), Pt(tdt)(pbpcd), and Pt(tdt)(bpcd)', Journal of Inorganic and Organometallic Polymers and Materials, vol. 20, no. 3, pp. 457-467. https://doi.org/10.1007/s10904-010-9357-6

New Pt(II)(dithiolate) Compounds Possessing an Energetically Accessible Diphosphine-Based LUMO: Syntheses, Redox Properties, and Solid-State Structures of PtCl ₂(pbpcd), Pt(tdt)(pbpcd), and Pt(tdt)(bpcd). / Hunt, Sean W.; Yang, Li; Wang, Xiaoping et al.
In: Journal of Inorganic and Organometallic Polymers and Materials, Vol. 20, No. 3, 2010, p. 457-467.

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

TY - JOUR

T1 - New Pt(II)(dithiolate) Compounds Possessing an Energetically Accessible Diphosphine-Based LUMO

T2 - Syntheses, Redox Properties, and Solid-State Structures of PtCl 2(pbpcd), Pt(tdt)(pbpcd), and Pt(tdt)(bpcd)

AU - Hunt, Sean W.

AU - Yang, Li

AU - Wang, Xiaoping

AU - Nesterov, Vladimir

AU - Richmond, Michael G.

PY - 2010

Y1 - 2010

N2 - The new ligand 2-(pyren-1-ylidene)-4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (pbpcd) has been synthesized from the Knoevenagel condensation using 1-pyrenecarboxaldehyde with 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd). Displacement of the cod ligand in PtCl 2(cod) by pbpcd furnishes PtCl 2(pbpcd) (2) in near quantitative yield. Treatment of 2 with the dipotassium salt of toluene-3,4-dithiol (K 2tdt) affords the dithiolate compound Pt(tdt)(pbpcd) (3) as a 1:1 mixture of diastereomers. An alternative synthesis of 3 from Pt(tdt)(bpcd) (5) and 1-pyrenecarboxaldehyde also affords 3 in 23% yield. The pbpcd ligand and all new diphosphine-substituted compounds have been isolated and fully characterized in solution by IR and NMR spectroscopies, and the solid-state structures of 2·CH 2Cl 2, 3·toluene, and 5·CH 2Cl 2 established by X-ray diffraction analyses. The solid-state structure of each product exhibits a square-planar architecture at the metal center. The redox properties of the pbpcd ligand and the tdt-substituted compound 3 have been explored by cyclic and differential-pulse voltammetry, and these data are discussed with respect to extended Hückel MO calculations and the nature of the HOMO and LUMO levels in each compound.

AB - The new ligand 2-(pyren-1-ylidene)-4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (pbpcd) has been synthesized from the Knoevenagel condensation using 1-pyrenecarboxaldehyde with 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd). Displacement of the cod ligand in PtCl 2(cod) by pbpcd furnishes PtCl 2(pbpcd) (2) in near quantitative yield. Treatment of 2 with the dipotassium salt of toluene-3,4-dithiol (K 2tdt) affords the dithiolate compound Pt(tdt)(pbpcd) (3) as a 1:1 mixture of diastereomers. An alternative synthesis of 3 from Pt(tdt)(bpcd) (5) and 1-pyrenecarboxaldehyde also affords 3 in 23% yield. The pbpcd ligand and all new diphosphine-substituted compounds have been isolated and fully characterized in solution by IR and NMR spectroscopies, and the solid-state structures of 2·CH 2Cl 2, 3·toluene, and 5·CH 2Cl 2 established by X-ray diffraction analyses. The solid-state structure of each product exhibits a square-planar architecture at the metal center. The redox properties of the pbpcd ligand and the tdt-substituted compound 3 have been explored by cyclic and differential-pulse voltammetry, and these data are discussed with respect to extended Hückel MO calculations and the nature of the HOMO and LUMO levels in each compound.

KW - Diphosphine ligand

KW - Dithiolate ligand

KW - MO calculations

KW - Platinum compounds

KW - Redox chemistry

KW - X-ray crystallography

UR - http://www.scopus.com/inward/record.url?scp=77956013063&partnerID=8YFLogxK

U2 - 10.1007/s10904-010-9357-6

DO - 10.1007/s10904-010-9357-6

M3 - Article

AN - SCOPUS:77956013063

SN - 1574-1443

VL - 20

SP - 457

EP - 467

JO - Journal of Inorganic and Organometallic Polymers and Materials

JF - Journal of Inorganic and Organometallic Polymers and Materials

IS - 3

ER -