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 - http://www.scopus.com/inward/record.url?scp=0032859501&partnerID=8YFLogxK
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 -
