Pt as mediator of strong antiferromagnetic coupling between two CuII ions in a heteronuclear CuIIPtIICuII complex of the model nucleobase 1-methylcytosinate

Alexander Hegmans; Ennio Zangrando; Eva Freisinger; Fabio Pichierri; Lucio Randaccio; Carlo Mealli; Michael Gerdan; Alfred X. Trautwein; Bernhard Lippert

doi:10.1002/(SICI)1521-3765(19991001)5:10<3010::AID-CHEM3010>3.0.CO;2-O

Pt as mediator of strong antiferromagnetic coupling between two Cu^II ions in a heteronuclear Cu^IIPt^IICu^II complex of the model nucleobase 1-methylcytosinate

Alexander Hegmans, Ennio Zangrando, Eva Freisinger, Fabio Pichierri, Lucio Randaccio, Carlo Mealli, Michael Gerdan, Alfred X. Trautwein, Bernhard Lippert^*

^*Corresponding author for this work

Institute of Physics

36 Citations (Scopus)

Abstract

The tetrakis(1-methylcytosine) complex [Pt(1-MeC-N3)₄](NO₃)₂ (1) in its head-tail-head-tail (htht) rotamer form binds upon deprotonation of the exocyclic amino group of 1-MeC, two Cu^II at either side of the central Pt^II to give trinuclear cations [Pt(1-MeC^-)₄-Cu₂X₂]ⁿ⁺ (2) with X = Cl^-, H₂O, NSC^-, N₃^-. X-ray crystal structure analyses of [Pt(1-MeC^-)₄Cu2(Cl)_1.6(H₂O) _0.4(NO₃V_0.4-1.6H₂O (2a) and [Pt(1-MeC^-)₄Cu₂-(H₂O) ₂](NO₃)₂ · 3H₂O (2b) reveal short Cu-Pt distances of 2.519(2)-2.531(2)Å. These compounds are diamagnetic as a result of the strong exchange interaction (J = 980 ± 30 cm^-1 (2a)), despite a separation of approximately 5 Å between the Cu^II centers. MO considerations are in agreement with the assumption that Pt^II acts as a mediator between the two Cu^II centers. A second trinuclear complex derived from the hhhh rotamer of 1 containing both Co^III and Na⁺ [Pt(1-Me-C^-)₄Co(H₂O)Na] (NO₃)₂·2 H₂O (3) has been isolated in very low yield and characterized by X-ray structure analysis. The Co^III center is bound to four amide N atoms and forms a bond to Pt (2.402(2) Å), whereas the Na⁺ ion is bound to the four oxygen atoms of the nucleobase. A general route for the preparation of heteronuclear MPtM and MPtM' compounds is described.

Original language	English
Journal	Chemistry - A European Journal
Volume	5
Issue number	10
Pages (from-to)	3010-3018
Number of pages	9
ISSN	0947-6539
DOIs	https://doi.org/10.1002/(SICI)1521-3765(19991001)5:10<3010::AID-CHEM3010>3.0.CO;2-O
Publication status	Published - 01.10.1999

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10.1002/(SICI)1521-3765(19991001)5:10<3010::AID-CHEM3010>3.0.CO;2-O

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Hegmans, A., Zangrando, E., Freisinger, E., Pichierri, F., Randaccio, L., Mealli, C., Gerdan, M., Trautwein, A. X., & Lippert, B. (1999). Pt as mediator of strong antiferromagnetic coupling between two Cu^II ions in a heteronuclear Cu^IIPt^IICu^II complex of the model nucleobase 1-methylcytosinate. Chemistry - A European Journal, 5(10), 3010-3018. https://doi.org/10.1002/(SICI)1521-3765(19991001)5:10<3010::AID-CHEM3010>3.0.CO;2-O

@article{4f8ea81e1dd847868ed34c73f077d5ba,

title = "Pt as mediator of strong antiferromagnetic coupling between two CuII ions in a heteronuclear CuIIPtIICuII complex of the model nucleobase 1-methylcytosinate",

abstract = "The tetrakis(1-methylcytosine) complex [Pt(1-MeC-N3)4](NO3)2 (1) in its head-tail-head-tail (htht) rotamer form binds upon deprotonation of the exocyclic amino group of 1-MeC, two CuII at either side of the central PtII to give trinuclear cations [Pt(1-MeC-)4-Cu2X2]n+ (2) with X = Cl-, H2O, NSC-, N3-. X-ray crystal structure analyses of [Pt(1-MeC-)4Cu2(Cl)1.6(H2O) 0.4(NO3V0.4-1.6H2O (2a) and [Pt(1-MeC-)4Cu2-(H2O) 2](NO3)2 · 3H2O (2b) reveal short Cu-Pt distances of 2.519(2)-2.531(2){\AA}. These compounds are diamagnetic as a result of the strong exchange interaction (J = 980 ± 30 cm-1 (2a)), despite a separation of approximately 5 {\AA} between the CuII centers. MO considerations are in agreement with the assumption that PtII acts as a mediator between the two CuII centers. A second trinuclear complex derived from the hhhh rotamer of 1 containing both CoIII and Na+ [Pt(1-Me-C-)4Co(H2O)Na] (NO3)2·2 H2O (3) has been isolated in very low yield and characterized by X-ray structure analysis. The CoIII center is bound to four amide N atoms and forms a bond to Pt (2.402(2) {\AA}), whereas the Na+ ion is bound to the four oxygen atoms of the nucleobase. A general route for the preparation of heteronuclear MPtM and MPtM' compounds is described.",

author = "Alexander Hegmans and Ennio Zangrando and Eva Freisinger and Fabio Pichierri and Lucio Randaccio and Carlo Mealli and Michael Gerdan and Trautwein, \{Alfred X.\} and Bernhard Lippert",

year = "1999",

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doi = "10.1002/(SICI)1521-3765(19991001)5:10<3010::AID-CHEM3010>3.0.CO;2-O",

language = "English",

volume = "5",

pages = "3010--3018",

journal = "Chemistry - A European Journal",

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Hegmans, A, Zangrando, E, Freisinger, E, Pichierri, F, Randaccio, L, Mealli, C, Gerdan, M, Trautwein, AX & Lippert, B 1999, 'Pt as mediator of strong antiferromagnetic coupling between two Cu^II ions in a heteronuclear Cu^IIPt^IICu^II complex of the model nucleobase 1-methylcytosinate', Chemistry - A European Journal, vol. 5, no. 10, pp. 3010-3018. https://doi.org/10.1002/(SICI)1521-3765(19991001)5:10<3010::AID-CHEM3010>3.0.CO;2-O

Pt as mediator of strong antiferromagnetic coupling between two Cu^II ions in a heteronuclear Cu^IIPt^IICu^II complex of the model nucleobase 1-methylcytosinate. / Hegmans, Alexander; Zangrando, Ennio; Freisinger, Eva et al.
In: Chemistry - A European Journal, Vol. 5, No. 10, 01.10.1999, p. 3010-3018.

Research output: Journal Articles › Journal articles › Research › peer-review

TY - JOUR

T1 - Pt as mediator of strong antiferromagnetic coupling between two CuII ions in a heteronuclear CuIIPtIICuII complex of the model nucleobase 1-methylcytosinate

AU - Hegmans, Alexander

AU - Zangrando, Ennio

AU - Freisinger, Eva

AU - Pichierri, Fabio

AU - Randaccio, Lucio

AU - Mealli, Carlo

AU - Gerdan, Michael

AU - Trautwein, Alfred X.

AU - Lippert, Bernhard

PY - 1999/10/1

Y1 - 1999/10/1

N2 - The tetrakis(1-methylcytosine) complex [Pt(1-MeC-N3)4](NO3)2 (1) in its head-tail-head-tail (htht) rotamer form binds upon deprotonation of the exocyclic amino group of 1-MeC, two CuII at either side of the central PtII to give trinuclear cations [Pt(1-MeC-)4-Cu2X2]n+ (2) with X = Cl-, H2O, NSC-, N3-. X-ray crystal structure analyses of [Pt(1-MeC-)4Cu2(Cl)1.6(H2O) 0.4(NO3V0.4-1.6H2O (2a) and [Pt(1-MeC-)4Cu2-(H2O) 2](NO3)2 · 3H2O (2b) reveal short Cu-Pt distances of 2.519(2)-2.531(2)Å. These compounds are diamagnetic as a result of the strong exchange interaction (J = 980 ± 30 cm-1 (2a)), despite a separation of approximately 5 Å between the CuII centers. MO considerations are in agreement with the assumption that PtII acts as a mediator between the two CuII centers. A second trinuclear complex derived from the hhhh rotamer of 1 containing both CoIII and Na+ [Pt(1-Me-C-)4Co(H2O)Na] (NO3)2·2 H2O (3) has been isolated in very low yield and characterized by X-ray structure analysis. The CoIII center is bound to four amide N atoms and forms a bond to Pt (2.402(2) Å), whereas the Na+ ion is bound to the four oxygen atoms of the nucleobase. A general route for the preparation of heteronuclear MPtM and MPtM' compounds is described.

AB - The tetrakis(1-methylcytosine) complex [Pt(1-MeC-N3)4](NO3)2 (1) in its head-tail-head-tail (htht) rotamer form binds upon deprotonation of the exocyclic amino group of 1-MeC, two CuII at either side of the central PtII to give trinuclear cations [Pt(1-MeC-)4-Cu2X2]n+ (2) with X = Cl-, H2O, NSC-, N3-. X-ray crystal structure analyses of [Pt(1-MeC-)4Cu2(Cl)1.6(H2O) 0.4(NO3V0.4-1.6H2O (2a) and [Pt(1-MeC-)4Cu2-(H2O) 2](NO3)2 · 3H2O (2b) reveal short Cu-Pt distances of 2.519(2)-2.531(2)Å. These compounds are diamagnetic as a result of the strong exchange interaction (J = 980 ± 30 cm-1 (2a)), despite a separation of approximately 5 Å between the CuII centers. MO considerations are in agreement with the assumption that PtII acts as a mediator between the two CuII centers. A second trinuclear complex derived from the hhhh rotamer of 1 containing both CoIII and Na+ [Pt(1-Me-C-)4Co(H2O)Na] (NO3)2·2 H2O (3) has been isolated in very low yield and characterized by X-ray structure analysis. The CoIII center is bound to four amide N atoms and forms a bond to Pt (2.402(2) Å), whereas the Na+ ion is bound to the four oxygen atoms of the nucleobase. A general route for the preparation of heteronuclear MPtM and MPtM' compounds is described.

UR - https://www.scopus.com/pages/publications/0032859501

U2 - 10.1002/(SICI)1521-3765(19991001)5:10<3010::AID-CHEM3010>3.0.CO;2-O

DO - 10.1002/(SICI)1521-3765(19991001)5:10<3010::AID-CHEM3010>3.0.CO;2-O

M3 - Journal articles

AN - SCOPUS:0032859501

SN - 0947-6539

VL - 5

SP - 3010

EP - 3018

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 10

ER -

Hegmans A, Zangrando E, Freisinger E, Pichierri F, Randaccio L, Mealli C et al. Pt as mediator of strong antiferromagnetic coupling between two Cu^II ions in a heteronuclear Cu^IIPt^IICu^II complex of the model nucleobase 1-methylcytosinate. Chemistry - A European Journal. 1999 Oct 1;5(10):3010-3018. doi: 10.1002/(SICI)1521-3765(19991001)5:10<3010::AID-CHEM3010>3.0.CO;2-O

Pt as mediator of strong antiferromagnetic coupling between two Cu^II ions in a heteronuclear Cu^IIPt^IICu^II complex of the model nucleobase 1-methylcytosinate

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