Redox, transmetalation, and stacking properties of tetrathiafulvalene-2,3,6,7-tetrathiolate bridged tin, nickel, and palladium compounds

Literature Information

Publication Date 2019-12-04
DOI 10.1039/C9SC04381K
Impact Factor 9.825
Authors

Jiaze Xie, Jan-Niklas Boyn, Alexander S. Filatov, Andrew J. McNeece, David A. Mazziotti, John S. Anderson


View Original

Abstract

Here we report that capping the molecule TTFtt (TTFtt = tetrathiafulvalene-2,3,6,7-tetrathiolate) with dialkyl tin groups enables the isolation of a stable series of redox congeners and facile transmetalation to Ni and Pd. TTFtt has been proposed as an attractive building block for molecular materials for two decades as it combines the redox chemistry of TTF and dithiolene units. TTFttH4, however, is inherently unstable and the incorporation of TTFtt units into complexes or materials typically proceeds through the in situ generation of the tetraanion TTFtt4−. Capping of TTFtt4− with Bu2Sn2+ units dramatically improves the stability of the TTFtt moiety and furthermore enables the isolation of a redox series where the TTF core carries the formal charges of 0, +1, and +2. All of these redox congeners show efficient and clean transmetalation to Ni and Pd resulting in an analogous series of bimetallic complexes capped by 1,2-bis(diphenylphosphino)ethane (dppe) ligands. Furthermore, by using the same transmetalation method, we synthesized analogous palladium complexes capped by 1,1′-bis(diphenylphosphino)ferrocene (dppf) which had been previously reported. All of these species have been thoroughly characterized through a systematic survey of chemical and electronic properties by techniques including cyclic voltammetry (CV), ultraviolet-visible-near infrared spectroscopy (UV-vis-NIR), electron paramagnetic resonance spectroscopy (EPR), nuclear magnetic resonance spectroscopy (NMR) and X-ray diffraction (XRD). These detailed synthetic and spectroscopic studies highlight important differences between the transmetalation strategy presented here and previously reported synthetic methods for the installation of TTFtt. In addition, the utility of this stabilization strategy can be illustrated by the observation of unusual TTF radical–radical packing in the solid state and dimerization in the solution state. Theoretical calculations based on variational 2-electron reduced density matrix methods have been used to investigate these unusual interactions and illustrate fundamentally different levels of covalency and overlap depending on the orientations of the TTF cores. Taken together, this work demonstrates that tin-capped TTFtt units are ideal reagents for the installation of redox-tunable TTFtt ligands enabling the generation of entirely new geometric and electronic structures.

Related Literature

Unfolding and refolding details of lysozyme in the presence of β-casein micelles

Fu-Gen Wu, Jun-Jie Luo, Zhi-Wu Yu

2011-01-24 Paper

DOI: 10.1039/C0CP01184C

Mechanistic differences between methanol and dimethyl ethercarbonylation in side pockets and large channels of mordenite

Mercedes Boronat, Cristina Martínez, Avelino Corma

2011-01-19 Paper

DOI: 10.1039/C0CP01996H

Back cover

Front/Back Matter

DOI: 10.1039/C1CP90010B

A novel lyotropic liquid crystal formed by triphilic star-polyphiles: hydrophilic/oleophilic/fluorophilic rods arranged in a 12.6.4. tiling‡

Liliana de Campo, Trond Varslot, Minoo J. Moghaddam, Jacob J. K. Kirkensgaard, Kell Mortensen, Stephen T. Hyde

2010-11-22 Paper

DOI: 10.1039/C0CP01201G

Pseudo Jahn–Teller origin of cis–trans and other conformational changes. The role of double bonds

Pablo Garcia-Fernandez, Yang Liu, Isaac B. Bersuker, James E. Boggs

2011-01-17 Paper

DOI: 10.1039/C0CP00900H

Improved light olefin yield from methyl bromide coupling over modified SAPO-34 molecular sieves

Aihua Zhang, Shouli Sun, Zachary J. A. Komon, Neil Osterwalder, Sagar Gadewar, Peter Stoimenov, Daniel J. Auerbach, Galen D. Stucky, Eric W. McFarland

2011-01-04 Paper

DOI: 10.1039/C0CP01985B

Structure and binding of the H4 histone tail and the effects of lysine 16 acetylation

Darren Yang, Gaurav Arya

2010-12-15 Paper

DOI: 10.1039/C0CP01487G

Ion conducting particle networks in liquids: modeling of network percolation and stability

Anna Jarosik, Uwe Traub, Joachim Maier, Armin Bunde

2010-12-23 Communication

DOI: 10.1039/C0CP01870H

Fullerene derivative acceptors for high performance polymer solar cells

Youjun He, Yongfang Li

2010-12-22 Perspective

DOI: 10.1039/C0CP01178A

You might also like

Compound Q&A

What are the main uses of 1H-Indazole-6-carbonitrile (CAS: 141290-59-7)?

1H-Indazole-6-carbonitrile finds applications in pharmaceuticals, where it serve...

141290-59-71H-Indazole-6-carbon...
Compound Q&A

How should waste containing Dioctyl (2E)-2-butenedioate (CAS: 2997-85-5) be handled?

Waste containing Dioctyl (2E)-2-butenedioate (CAS: 2997-85-5) should be collecte...

2997-85-5Dioctyl (2E)-2-buten...
Compound Q&A

What industries use Sodium [(1,2-benzoxazol-3-ylmethyl)sulfonyl]azanide (CAS: 68291-98-5)?

Sodium [(1,2-benzoxazol-3-ylmethyl)sulfonyl]azanide is primarily used in pharmac...

68291-98-5Sodium [(1,2-benzoxa...
Compound Q&A

Are there alternatives to Dimethyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,6-pyridinedicarboxylate (CAS: 741709-66-0) in synthesis?

Dimethyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,6-pyridinedicarboxyla...

741709-66-0Dimethyl 4-(4,4,5,5-...
Compound Q&A

How should waste containing 2-Fluoro-6-hydrazinopyridine (CAS: 80714-39-2) be handled?

Waste containing 2-Fluoro-6-hydrazinopyridine (CAS: 80714-39-2) should be manage...

80714-39-22-Fluoro-6-hydrazino...
Compound Q&A

What is 6-Formyl-2-pyridinecarboxylic acid (CAS: 499214-11-8)?

6-Formyl-2-pyridinecarboxylic acid is an organic compound with the molecular for...

499214-11-86-Formyl-2-pyridinec...
900874-91-13-(3,4-dimethoxyphen...
Compound Q&A

How is 9H-Tribenzo[b,d,f]azepine (CAS: 29875-73-8) typically synthesized?

9H-Tribenzo[b,d,f]azepine is typically synthesized via a multi-step process invo...

29875-73-89H-Tribenzo[b,d,f]az...
Compound Q&A

How is 1-Cyclopropyl-7-ethoxy-6-fluoro-8-methoxy-4-oxo-1,4-dihydro-3-quinolinecarboxylic acid (CAS: 1797982-51-4) typically synthesized?

1-Cyclopropyl-7-ethoxy-6-fluoro-8-methoxy-4-oxo-1,4-dihydro-3-quinolinecarboxyli...

1797982-51-41-Cyclopropyl-7-etho...
Compound Q&A

How should waste containing Methyl 3-oxo-1,2,3,4-tetrahydro-6-quinoxalinecarboxylate (CAS: 671820-52-3) be handled?

Waste containing Methyl 3-oxo-1,2,3,4-tetrahydro-6-quinoxalinecarboxylate (CAS: ...

671820-52-3Methyl 3-oxo-1,2,3,4...

Source Journal

Chemical Science

Chemical Science
CiteScore: 14.4
Self-citation Rate: 3.9%
Articles per Year: 1413

Our journal has a wide-ranging scope which covers the full breadth of the chemical sciences. The research we publish contains the sorts of novel ideas, challenging questions and progressive thinking that bring undiscovered breakthroughs within reach. Your paper could focus on a single area, or cross many. It could be beyond the accepted bounds of the chemical sciences. It might address an immediate challenge, contribute to a future breakthrough or be wholly conceptual. We’re a team from every field of the chemical sciences, and know from experience that breakthroughs that drive the solutions to global challenges can come from anywhere, at any time. You could even start an entirely new area of research. Too bold? Too progressive? No such thing

Recommended Compounds

Recommended Suppliers

Disclaimer
This page provides academic journal information for reference and research purposes only. We are not affiliated with any journal publishers and do not handle publication submissions. For publication-related inquiries, please contact the respective journal publishers directly.
If you notice any inaccuracies in the information displayed, please contact us at support@chemtradehub.com. We will promptly review and address your concerns.