A β-ketoiminato palladium(II) complex for palladium deposition

Andrea Preuß, Marcus Korb, Tobias Rüffer, Jörn Bankwitz, Colin Georgi, Alexander Jakob, Stefan E. Schulz, Heinrich Lang

Research output: Contribution to journalArticle

Abstract

The β-ketoiminato complex [Pd(OAc)L] (3) can be synthesized by the reaction of bis(benzoylacetone)diethylenetriamine (1, = LH) with [Pd(OAc)2] (2). The structure of 3 in the solid state has been determined by single X-ray diffraction analysis. Complex 3 crystallizes as a dimer (32), which is formed by hydrogen bonds between NH and OOAc functionalities of two adjacent ligands. Each of the Pd atoms is complexed by one ON2 donor unit of the polydentate ligand L- and an acetate group. Pd-Pd interactions and hydrogen bond formation between a NH and the C=O acetate moiety lead to a [4 + 2] coordination at Pd. The non-coordinated part of L exists in its β-keto-enamine form. The thermal decomposition behavior of 32 was studied by TG (thermogravimetry) and TG-MS showing that 32 decomposes between 200 and 500°C independent of the applied atmosphere. Under oxygen PdO is produced, while under argon Pd is formed as confirmed by PXRD measurements. Complex 32 was applied as a spin-coating precursor (conc. 0.1 mol L-1, volume 1.5 mL, 3000 rpm, deposition time 6 min, heating rate 50 K min-1, holding time 60 min (Ar) and 120 min (air) at T = 800°C). The as-obtained samples are characterized by granulated particles of Pd/PdO on the substrate surface. EDX (energy-dispersive X-ray spectroscopy) and XPS (X-ray photoelectron spectroscopy) measurements confirmed the formation of Pd (Ar) or PdO (O2) with up to 12 mol% C impurity.

Original languageEnglish
Pages (from-to)901-912
Number of pages12
JournalZeitschrift fur Naturforschung - Section B Journal of Chemical Sciences
Volume74
Issue number11-12
DOIs
Publication statusPublished - 4 Dec 2019

Fingerprint

Palladium
Thermogravimetric analysis
Hydrogen bonds
Acetates
Ligands
Argon
Spin coating
Heating rate
Dimers
X ray diffraction analysis
Pyrolysis
X ray photoelectron spectroscopy
Impurities
Oxygen
Atoms
Substrates
Air
benzoylacetone
palladium(II) acetate
X-Ray Emission Spectrometry

Cite this

Preuß, Andrea ; Korb, Marcus ; Rüffer, Tobias ; Bankwitz, Jörn ; Georgi, Colin ; Jakob, Alexander ; Schulz, Stefan E. ; Lang, Heinrich. / A β-ketoiminato palladium(II) complex for palladium deposition. In: Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences. 2019 ; Vol. 74, No. 11-12. pp. 901-912.
@article{8faaa1a54d50442cbf79751ee984758a,
title = "A β-ketoiminato palladium(II) complex for palladium deposition",
abstract = "The β-ketoiminato complex [Pd(OAc)L] (3) can be synthesized by the reaction of bis(benzoylacetone)diethylenetriamine (1, = LH) with [Pd(OAc)2] (2). The structure of 3 in the solid state has been determined by single X-ray diffraction analysis. Complex 3 crystallizes as a dimer (32), which is formed by hydrogen bonds between NH and OOAc functionalities of two adjacent ligands. Each of the Pd atoms is complexed by one ON2 donor unit of the polydentate ligand L- and an acetate group. Pd-Pd interactions and hydrogen bond formation between a NH and the C=O acetate moiety lead to a [4 + 2] coordination at Pd. The non-coordinated part of L exists in its β-keto-enamine form. The thermal decomposition behavior of 32 was studied by TG (thermogravimetry) and TG-MS showing that 32 decomposes between 200 and 500°C independent of the applied atmosphere. Under oxygen PdO is produced, while under argon Pd is formed as confirmed by PXRD measurements. Complex 32 was applied as a spin-coating precursor (conc. 0.1 mol L-1, volume 1.5 mL, 3000 rpm, deposition time 6 min, heating rate 50 K min-1, holding time 60 min (Ar) and 120 min (air) at T = 800°C). The as-obtained samples are characterized by granulated particles of Pd/PdO on the substrate surface. EDX (energy-dispersive X-ray spectroscopy) and XPS (X-ray photoelectron spectroscopy) measurements confirmed the formation of Pd (Ar) or PdO (O2) with up to 12 mol{\%} C impurity.",
keywords = "palladium, solid-state -structure, spin-coating, thermal behavior, β-ketoiminato",
author = "Andrea Preu{\ss} and Marcus Korb and Tobias R{\"u}ffer and J{\"o}rn Bankwitz and Colin Georgi and Alexander Jakob and Schulz, {Stefan E.} and Heinrich Lang",
year = "2019",
month = "12",
day = "4",
doi = "10.1515/znb-2019-0172",
language = "English",
volume = "74",
pages = "901--912",
journal = "ZEITSCHRIFT FUR NATURFORSCHUNG SECTION B-A JOURNAL OF CHEMICAL SCIENCES",
issn = "0932-0776",
publisher = "Verlag der Zeitschrift fur Naturforschung",
number = "11-12",

}

Preuß, A, Korb, M, Rüffer, T, Bankwitz, J, Georgi, C, Jakob, A, Schulz, SE & Lang, H 2019, 'A β-ketoiminato palladium(II) complex for palladium deposition' Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, vol. 74, no. 11-12, pp. 901-912. https://doi.org/10.1515/znb-2019-0172

A β-ketoiminato palladium(II) complex for palladium deposition. / Preuß, Andrea; Korb, Marcus; Rüffer, Tobias; Bankwitz, Jörn; Georgi, Colin; Jakob, Alexander; Schulz, Stefan E.; Lang, Heinrich.

In: Zeitschrift fur Naturforschung - Section B Journal of Chemical Sciences, Vol. 74, No. 11-12, 04.12.2019, p. 901-912.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A β-ketoiminato palladium(II) complex for palladium deposition

AU - Preuß, Andrea

AU - Korb, Marcus

AU - Rüffer, Tobias

AU - Bankwitz, Jörn

AU - Georgi, Colin

AU - Jakob, Alexander

AU - Schulz, Stefan E.

AU - Lang, Heinrich

PY - 2019/12/4

Y1 - 2019/12/4

N2 - The β-ketoiminato complex [Pd(OAc)L] (3) can be synthesized by the reaction of bis(benzoylacetone)diethylenetriamine (1, = LH) with [Pd(OAc)2] (2). The structure of 3 in the solid state has been determined by single X-ray diffraction analysis. Complex 3 crystallizes as a dimer (32), which is formed by hydrogen bonds between NH and OOAc functionalities of two adjacent ligands. Each of the Pd atoms is complexed by one ON2 donor unit of the polydentate ligand L- and an acetate group. Pd-Pd interactions and hydrogen bond formation between a NH and the C=O acetate moiety lead to a [4 + 2] coordination at Pd. The non-coordinated part of L exists in its β-keto-enamine form. The thermal decomposition behavior of 32 was studied by TG (thermogravimetry) and TG-MS showing that 32 decomposes between 200 and 500°C independent of the applied atmosphere. Under oxygen PdO is produced, while under argon Pd is formed as confirmed by PXRD measurements. Complex 32 was applied as a spin-coating precursor (conc. 0.1 mol L-1, volume 1.5 mL, 3000 rpm, deposition time 6 min, heating rate 50 K min-1, holding time 60 min (Ar) and 120 min (air) at T = 800°C). The as-obtained samples are characterized by granulated particles of Pd/PdO on the substrate surface. EDX (energy-dispersive X-ray spectroscopy) and XPS (X-ray photoelectron spectroscopy) measurements confirmed the formation of Pd (Ar) or PdO (O2) with up to 12 mol% C impurity.

AB - The β-ketoiminato complex [Pd(OAc)L] (3) can be synthesized by the reaction of bis(benzoylacetone)diethylenetriamine (1, = LH) with [Pd(OAc)2] (2). The structure of 3 in the solid state has been determined by single X-ray diffraction analysis. Complex 3 crystallizes as a dimer (32), which is formed by hydrogen bonds between NH and OOAc functionalities of two adjacent ligands. Each of the Pd atoms is complexed by one ON2 donor unit of the polydentate ligand L- and an acetate group. Pd-Pd interactions and hydrogen bond formation between a NH and the C=O acetate moiety lead to a [4 + 2] coordination at Pd. The non-coordinated part of L exists in its β-keto-enamine form. The thermal decomposition behavior of 32 was studied by TG (thermogravimetry) and TG-MS showing that 32 decomposes between 200 and 500°C independent of the applied atmosphere. Under oxygen PdO is produced, while under argon Pd is formed as confirmed by PXRD measurements. Complex 32 was applied as a spin-coating precursor (conc. 0.1 mol L-1, volume 1.5 mL, 3000 rpm, deposition time 6 min, heating rate 50 K min-1, holding time 60 min (Ar) and 120 min (air) at T = 800°C). The as-obtained samples are characterized by granulated particles of Pd/PdO on the substrate surface. EDX (energy-dispersive X-ray spectroscopy) and XPS (X-ray photoelectron spectroscopy) measurements confirmed the formation of Pd (Ar) or PdO (O2) with up to 12 mol% C impurity.

KW - palladium

KW - solid-state -structure

KW - spin-coating

KW - thermal behavior

KW - β-ketoiminato

UR - http://www.scopus.com/inward/record.url?scp=85077342709&partnerID=8YFLogxK

U2 - 10.1515/znb-2019-0172

DO - 10.1515/znb-2019-0172

M3 - Article

VL - 74

SP - 901

EP - 912

JO - ZEITSCHRIFT FUR NATURFORSCHUNG SECTION B-A JOURNAL OF CHEMICAL SCIENCES

JF - ZEITSCHRIFT FUR NATURFORSCHUNG SECTION B-A JOURNAL OF CHEMICAL SCIENCES

SN - 0932-0776

IS - 11-12

ER -