Reversible photo-isomerization of: cis -[Pd(L-κ S, O)2] (HL = N, N -diethyl- N ′-1-naphthoylthiourea) to trans -[Pd(L-κ S, O)2] and the unprecedented formation of trans -[Pd(L-κ S, N)2] in solution

Henry A. Nkabyo; Barbara Procacci; Simon B. Duckett; Klaus R. Koch

doi:10.1039/c9dt03672e

Reversible photo-isomerization of: cis -[Pd(L-κ S, O)₂] (HL = N, N -diethyl- N ′-1-naphthoylthiourea) to trans -[Pd(L-κ S, O)₂] and the unprecedented formation of trans -[Pd(L-κ S, N)₂] in solution

Henry A. Nkabyo, Barbara Procacci, Simon B. Duckett, Klaus R. Koch^*

^*Corresponding author for this work

Chemistry

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

Abstract

Upon ex situ UV-visible light irradiation, complex cis-bis(N,N-diethyl-N′-naphthoylthioureato)-palladium(ii), cis-[Pd(L-κS,O)₂], undergoes isomerization in acetonitrile-d₃ and chloroform-d to yield trans-[Pd(L-κS,O)₂] which then rearranges thermally to novel trans-[Pd(L-κS,N)₂] prior to reverting thermally to the cis isomer in the absence of light. The thermal isomerization rate is highly solvent dependent and harnessed to enable each of these three geometric isomers to be isolated and characterized by ¹H NMR spectroscopy, X-ray crystallography, melting point and thermal analysis. The formation of the trans-[Pd(L-κS,N)₂] isomer as part of this isomerization has only been observed with the sterically demanding cis-bis(N,N-diethyl-N′-(naphthoylthioureato)palladium(ii) precursor based on our knowledge to date. In situ irradiation with monochromatic laser light (λ = 355 nm) coupled to ¹H NMR spectroscopy of solutions of cis-[Pd(L-κS,O)₂] in acetonitrile-d₃ supports the ex situ photo-induced isomerization experiments.

Original language	English
Pages (from-to)	17241-17251
Number of pages	11
Journal	Dalton Transactions
Volume	48
Issue number	46
Early online date	7 Nov 2019
DOIs	https://doi.org/10.1039/c9dt03672e
Publication status	E-pub ahead of print - 7 Nov 2019

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© The Royal Society of Chemistry 2019. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.

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10.1039/c9dt03672e

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Cite this

@article{2b02a657a27f4c1aa75889c323ca44ba,

title = "Reversible photo-isomerization of: cis -[Pd(L-κ S, O)2] (HL = N, N -diethyl- N ′-1-naphthoylthiourea) to trans -[Pd(L-κ S, O)2] and the unprecedented formation of trans -[Pd(L-κ S, N)2] in solution",

abstract = "Upon ex situ UV-visible light irradiation, complex cis-bis(N,N-diethyl-N′-naphthoylthioureato)-palladium(ii), cis-[Pd(L-κS,O)2], undergoes isomerization in acetonitrile-d3 and chloroform-d to yield trans-[Pd(L-κS,O)2] which then rearranges thermally to novel trans-[Pd(L-κS,N)2] prior to reverting thermally to the cis isomer in the absence of light. The thermal isomerization rate is highly solvent dependent and harnessed to enable each of these three geometric isomers to be isolated and characterized by 1H NMR spectroscopy, X-ray crystallography, melting point and thermal analysis. The formation of the trans-[Pd(L-κS,N)2] isomer as part of this isomerization has only been observed with the sterically demanding cis-bis(N,N-diethyl-N′-(naphthoylthioureato)palladium(ii) precursor based on our knowledge to date. In situ irradiation with monochromatic laser light (λ = 355 nm) coupled to 1H NMR spectroscopy of solutions of cis-[Pd(L-κS,O)2] in acetonitrile-d3 supports the ex situ photo-induced isomerization experiments.",

author = "Nkabyo, {Henry A.} and Barbara Procacci and Duckett, {Simon B.} and Koch, {Klaus R.}",

note = "{\textcopyright} The Royal Society of Chemistry 2019. This is an author-produced version of the published paper. Uploaded in accordance with the publisher{\textquoteright}s self-archiving policy. Further copying may not be permitted; contact the publisher for details. ",

year = "2019",

month = nov,

day = "7",

doi = "10.1039/c9dt03672e",

language = "English",

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journal = "Dalton Transactions",

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publisher = "The Royal Society of Chemistry",

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Reversible photo-isomerization of: cis -[Pd(L-κ S, O)₂] (HL = N, N -diethyl- N ′-1-naphthoylthiourea) to trans -[Pd(L-κ S, O)₂] and the unprecedented formation of trans -[Pd(L-κ S, N)₂] in solution. / Nkabyo, Henry A.; Procacci, Barbara ; Duckett, Simon B. et al.
In: Dalton Transactions, Vol. 48, No. 46, 07.11.2019, p. 17241-17251.

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

TY - JOUR

T1 - Reversible photo-isomerization of

T2 - cis -[Pd(L-κ S, O)2] (HL = N, N -diethyl- N ′-1-naphthoylthiourea) to trans -[Pd(L-κ S, O)2] and the unprecedented formation of trans -[Pd(L-κ S, N)2] in solution

AU - Nkabyo, Henry A.

AU - Procacci, Barbara

AU - Duckett, Simon B.

AU - Koch, Klaus R.

N1 - © The Royal Society of Chemistry 2019. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.

PY - 2019/11/7

Y1 - 2019/11/7

N2 - Upon ex situ UV-visible light irradiation, complex cis-bis(N,N-diethyl-N′-naphthoylthioureato)-palladium(ii), cis-[Pd(L-κS,O)2], undergoes isomerization in acetonitrile-d3 and chloroform-d to yield trans-[Pd(L-κS,O)2] which then rearranges thermally to novel trans-[Pd(L-κS,N)2] prior to reverting thermally to the cis isomer in the absence of light. The thermal isomerization rate is highly solvent dependent and harnessed to enable each of these three geometric isomers to be isolated and characterized by 1H NMR spectroscopy, X-ray crystallography, melting point and thermal analysis. The formation of the trans-[Pd(L-κS,N)2] isomer as part of this isomerization has only been observed with the sterically demanding cis-bis(N,N-diethyl-N′-(naphthoylthioureato)palladium(ii) precursor based on our knowledge to date. In situ irradiation with monochromatic laser light (λ = 355 nm) coupled to 1H NMR spectroscopy of solutions of cis-[Pd(L-κS,O)2] in acetonitrile-d3 supports the ex situ photo-induced isomerization experiments.

AB - Upon ex situ UV-visible light irradiation, complex cis-bis(N,N-diethyl-N′-naphthoylthioureato)-palladium(ii), cis-[Pd(L-κS,O)2], undergoes isomerization in acetonitrile-d3 and chloroform-d to yield trans-[Pd(L-κS,O)2] which then rearranges thermally to novel trans-[Pd(L-κS,N)2] prior to reverting thermally to the cis isomer in the absence of light. The thermal isomerization rate is highly solvent dependent and harnessed to enable each of these three geometric isomers to be isolated and characterized by 1H NMR spectroscopy, X-ray crystallography, melting point and thermal analysis. The formation of the trans-[Pd(L-κS,N)2] isomer as part of this isomerization has only been observed with the sterically demanding cis-bis(N,N-diethyl-N′-(naphthoylthioureato)palladium(ii) precursor based on our knowledge to date. In situ irradiation with monochromatic laser light (λ = 355 nm) coupled to 1H NMR spectroscopy of solutions of cis-[Pd(L-κS,O)2] in acetonitrile-d3 supports the ex situ photo-induced isomerization experiments.

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U2 - 10.1039/c9dt03672e

DO - 10.1039/c9dt03672e

M3 - Article

C2 - 31730138

AN - SCOPUS:85075679452

SN - 1477-9234

VL - 48

SP - 17241

EP - 17251

JO - Dalton Transactions

JF - Dalton Transactions

IS - 46

ER -