Solvent-dependent reactivity and photochemistry of dinuclear and mononuclear platinum (IV) azido triazaolato complexes

Kezi Yao; Arnau Bertran; Jacques Morgan; Charlotte Greenhalgh; Katharina Edkins; Alice Bowen; Nicola J. Farrer

doi:10.1002/ejic.202100041

Solvent-dependent reactivity and photochemistry of dinuclear and mononuclear platinum (IV) azido triazaolato complexes

Kezi Yao, Arnau Bertran, Jacques Morgan, Charlotte Greenhalgh, Katharina Edkins, Alice Bowen, Nicola J. Farrer

Strathclyde Institute Of Pharmacy And Biomedical Sciences

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Abstract

Reaction between the platinum(IV) azido complex trans,trans,trans-[Pt(py)2(N3)2(OH)2] (1) and 1,4-diphenyl-2-butyne-1,4-dione 2 in MeCN produces the intermediate peroxide-bridged dimeric platinum(IV) azido triazolato species (5), which has been characterised by X-ray crystallography. However, if the reaction between 1 and 2 is conducted in MeOH it results in decomposition. Over time in MeCN, dimer (5) converts into mononuclear complexes trans,trans,trans-[Pt(py)2(N3)(triazole)(OH)2] (3 a/3 b), which are in dynamic exchange. If resuspended in protic solvents (MeOH,H2O), 3 a/3 b undergo a slow (22 d) irreversible rearrangement to a cyclised platinum(IV) species 4 which contains a formally N,O-chelated ligand. Conversion of 3 a/3 b to 4 in d4-MeOH can be accelerated (384x) by irradiation with visible light, although continued irradiation also produces N3. and OH. radicals, and the [4-N3]+ species can be readily detected by ESI-MS. Solvent choice significantly effects both the cycloaddition reaction between 1 and 2, and the stability of the resultant complexes.

Original language	English
Pages (from-to)	1397-1404
Number of pages	8
Journal	European Journal of Inorganic Chemistry
Volume	2021
Issue number	14
Early online date	1 Mar 2021
DOIs	https://doi.org/10.1002/ejic.202100041
Publication status	Published - 15 Apr 2021

Funding

Funding Information: This work was supported by the Wellcome Trust (201406/Z/16/Z), Cancer Research UK (CR-UK) grant number C5255/A18085, through the Cancer Research UK Oxford Centre and the John Fell Fund. NF thanks Dr. Alan Kenwright and Profs. Stephen Faulkner and Andrew Weller for helpful discussions. EPR measurements were performed in the Centre for Advanced Electron Spin Resonance at the University of Oxford supported by the EPSRC (EP/L011972/1). A.M.B. gratefully acknowledges her fellowship support from the Royal Society and EPSRC for a Dorothy Hodgkin Fellowship (DH160004), and A.M.B and A.B acknowledge the support from the Royal Society Grant for Research Fellows (RGF80099).

Keywords

Azides
Photoactivity
Platinum
Radicals
Structure elucidation

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10.1002/ejic.202100041Licence: CC BY 4.0

Eur J Inorg Chem - 2021 - Yao - Solvent‐Dependent Reactivity and Photochemistry of Dinuclear and Mononuclear Platinum IV Final published version, 970 KBLicence: CC BY 4.0

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title = "Solvent-dependent reactivity and photochemistry of dinuclear and mononuclear platinum (IV) azido triazaolato complexes",

abstract = "Reaction between the platinum(IV) azido complex trans,trans,trans-[Pt(py)2(N3)2(OH)2] (1) and 1,4-diphenyl-2-butyne-1,4-dione 2 in MeCN produces the intermediate peroxide-bridged dimeric platinum(IV) azido triazolato species (5), which has been characterised by X-ray crystallography. However, if the reaction between 1 and 2 is conducted in MeOH it results in decomposition. Over time in MeCN, dimer (5) converts into mononuclear complexes trans,trans,trans-[Pt(py)2(N3)(triazole)(OH)2] (3 a/3 b), which are in dynamic exchange. If resuspended in protic solvents (MeOH,H2O), 3 a/3 b undergo a slow (22 d) irreversible rearrangement to a cyclised platinum(IV) species 4 which contains a formally N,O-chelated ligand. Conversion of 3 a/3 b to 4 in d4-MeOH can be accelerated (384x) by irradiation with visible light, although continued irradiation also produces N3. and OH. radicals, and the [4-N3]+ species can be readily detected by ESI-MS. Solvent choice significantly effects both the cycloaddition reaction between 1 and 2, and the stability of the resultant complexes.",

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AU - Yao, Kezi

AU - Bertran, Arnau

AU - Morgan, Jacques

AU - Greenhalgh, Charlotte

AU - Edkins, Katharina

AU - Bowen, Alice

AU - Farrer, Nicola J.

PY - 2021/4/15

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N2 - Reaction between the platinum(IV) azido complex trans,trans,trans-[Pt(py)2(N3)2(OH)2] (1) and 1,4-diphenyl-2-butyne-1,4-dione 2 in MeCN produces the intermediate peroxide-bridged dimeric platinum(IV) azido triazolato species (5), which has been characterised by X-ray crystallography. However, if the reaction between 1 and 2 is conducted in MeOH it results in decomposition. Over time in MeCN, dimer (5) converts into mononuclear complexes trans,trans,trans-[Pt(py)2(N3)(triazole)(OH)2] (3 a/3 b), which are in dynamic exchange. If resuspended in protic solvents (MeOH,H2O), 3 a/3 b undergo a slow (22 d) irreversible rearrangement to a cyclised platinum(IV) species 4 which contains a formally N,O-chelated ligand. Conversion of 3 a/3 b to 4 in d4-MeOH can be accelerated (384x) by irradiation with visible light, although continued irradiation also produces N3. and OH. radicals, and the [4-N3]+ species can be readily detected by ESI-MS. Solvent choice significantly effects both the cycloaddition reaction between 1 and 2, and the stability of the resultant complexes.

AB - Reaction between the platinum(IV) azido complex trans,trans,trans-[Pt(py)2(N3)2(OH)2] (1) and 1,4-diphenyl-2-butyne-1,4-dione 2 in MeCN produces the intermediate peroxide-bridged dimeric platinum(IV) azido triazolato species (5), which has been characterised by X-ray crystallography. However, if the reaction between 1 and 2 is conducted in MeOH it results in decomposition. Over time in MeCN, dimer (5) converts into mononuclear complexes trans,trans,trans-[Pt(py)2(N3)(triazole)(OH)2] (3 a/3 b), which are in dynamic exchange. If resuspended in protic solvents (MeOH,H2O), 3 a/3 b undergo a slow (22 d) irreversible rearrangement to a cyclised platinum(IV) species 4 which contains a formally N,O-chelated ligand. Conversion of 3 a/3 b to 4 in d4-MeOH can be accelerated (384x) by irradiation with visible light, although continued irradiation also produces N3. and OH. radicals, and the [4-N3]+ species can be readily detected by ESI-MS. Solvent choice significantly effects both the cycloaddition reaction between 1 and 2, and the stability of the resultant complexes.

KW - Azides

KW - Photoactivity

KW - Platinum

KW - Radicals

KW - Structure elucidation

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JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

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ER -

Solvent-dependent reactivity and photochemistry of dinuclear and mononuclear platinum (IV) azido triazaolato complexes

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