Effect of axial coordination on the electronic structure and biological activity of dirhodium(II,II) complexes

被引:56
作者
Aguirre, J. Dafhne
Lutterman, Daniel A.
Angeles-Boza, Alfredo M.
Dunbar, Kim R.
Turro, Claudia
机构
[1] Texas A&M Univ, Dept Chem, College Stn, TX 77843 USA
[2] Ohio State Univ, Dept Chem, Columbus, OH 43210 USA
关键词
D O I
10.1021/ic700708g
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The reactivities toward biomolecules of a series of three dirhodium(II,II) complexes that possess an increasing number of accessible axial coordination sites are compared. In cis-[Rh-2(OAc)(2)(np)(2)](2+) (1; np = 1,8-naphthyridine) both axial sites are available for coordination, whereas for cis-[Rh-2(OAc)(2)(np)(pynp)](2+) (2; pynp = 2-(2-pyridyl)1,8-naphthyridine) and cis-[Rh-2(OAc)(2)(pynp)(2)](2+) (3) the bridging pynp ligand blocks one and two of the axial coordination sites in the complexes, respectively. The electronic absorption spectra of the complexes are consistent with strong metal-to-ligand charge transfer transitions at low energy and ligand-centered peaks localized on the np and/or pynp ligands in the UV and near-UV regions. Time-dependent density functional theory calculations were used to aid in the assignments. The three complexes exhibit metal-centered oxidations and reductions, localized on the aromatic ligands. The ability of the complexes to stabilize duplex DNA and to inhibit transcription in vitro is greatly affected by the availability of an open axial coordination site. The present work shows that open axial coordination sites on the dirhodium complexes are necessary for biological activity.
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页码:7494 / 7502
页数:9
相关论文
共 129 条
[1]   ENERGY-ADJUSTED ABINITIO PSEUDOPOTENTIALS FOR THE 2ND AND 3RD ROW TRANSITION-ELEMENTS [J].
ANDRAE, D ;
HAUSSERMANN, U ;
DOLG, M ;
STOLL, H ;
PREUSS, H .
THEORETICA CHIMICA ACTA, 1990, 77 (02) :123-141
[2]   Dirhodium(II,II) complexes: Molecular characteristics that affect in vitro activity [J].
Angeles-Boza, Alfredo M. ;
Chifotides, Helen T. ;
Aguirre, J. Dafhne ;
Chouai, Abdellatif ;
Fu, Patty K. -L. ;
Dunbar, Kim R. ;
Turro, Claudia .
JOURNAL OF MEDICINAL CHEMISTRY, 2006, 49 (23) :6841-6847
[3]  
[Anonymous], 2002, SADABS VERS 2 03
[4]   Interactions between antiretrovirals and antineoplastic drug therapy [J].
Antoniou, T ;
Tseng, AL .
CLINICAL PHARMACOKINETICS, 2005, 44 (02) :111-145
[5]   Interligand interactions affecting specific metal bonding to nucleic acid bases:: the tetrakis(μ-trifluoroacetamidato)dirhodium(II)-cytosine system.: Crystal structures of [Rh2(CF3CONH)4(cytosine)] and [Rh2(CF3CONH)4(1-methylcytosine)2]•2H2O [J].
Aoki, K ;
Salam, MA .
INORGANICA CHIMICA ACTA, 2001, 316 (1-2) :50-58
[6]   Evidence for binding of dirhodium bis-acetate units to adjacent GG and AA sites on single-stranded DNA [J].
Asara, JM ;
Hess, JS ;
Lozada, E ;
Dunbar, KR ;
Allison, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (01) :8-13
[7]   Ecteinascidin 743: a novel anticancer drug with a unique mechanism of action [J].
Aune, GJ ;
Furuta, T ;
Pommier, Y .
ANTI-CANCER DRUGS, 2002, 13 (06) :545-555
[8]  
Barbour L.J., 2001, J SUPRAMOL CHEM, V1, P189
[9]  
BEAR JL, 1975, CANCER CHEMOTH REP 1, V59, P611
[10]  
BEAR JL, 1986, PRECIOUS METALS 1985, P337