Departamento de Química Inorgánica, Facultad de Química, Universidad de Murcia, 30071, Murcia, Spain.
Dalton Trans. 2009 Nov 21(43):9637-44. doi: 10.1039/b915427b. Epub 2009 Sep 26.
The synthesis of the new palladium and platinum complexes with 9-methylhypoxanthine (9-mhypH) of the type [M(dmba)(L)(9-mhypH-N7)]ClO(4) [dmba = N,C-chelating 2-(dimethylaminomethyl)phenyl; M = Pd or Pt; L = DMSO, PPh(3) or PTA (PTA = 1,3,5-Triaza-7-phosphaadamantane)] is reported. Pd(II) and Pt(II) complexes with the anion of 9-mhypH of the type [M(dmba)(L)(9-mhyp-N1)] [L = PPh(3) or PTA] have also been prepared. The crystal structures of [Pt(dmba)(PPh(3))(9-mhypH-N7)]ClO(4) and [Pt(dmba)(PPh(3))(9-mhyp-N1)] have been established by X-ray diffraction. The last complex is the first structurally authenticated example of N1 coordination of 9-methylhypoxanthine to platinum. DFT-based calculations at the BP86/def2TZVP level predict a most favourable interaction (both kinetically and thermodynamically) of the metal(II) centre with N7 in the neutral ligand 9-mhypH, but with N1 in the deprotonated ligand 9-mhyp(-) in agreement with the experimentally observed preference in neutral conditions or upon basic treatment, respectively.
报道了新型钯和铂配合物的合成，配体为 9-甲基次黄嘌呤（9-mhypH），其结构为[M(dmba)(L)(9-mhypH-N7)]ClO4 [dmba = N,C-螯合 2-(二甲氨基甲基)苯基；M = Pd 或 Pt；L = DMSO、PPh3 或 PTA（PTA = 1,3,5-三嗪-7-磷杂金刚烷）]。还制备了具有 9-mhypH 阴离子的 Pd(II)和 Pt(II)配合物，其结构为[M(dmba)(L)(9-mhyp-N1)] [L = PPh3 或 PTA]。通过 X 射线衍射确定了[Pt(dmba)(PPh3)(9-mhypH-N7)]ClO4 和 [Pt(dmba)(PPh3)(9-mhyp-N1)]的晶体结构。最后一个配合物是铂配位 9-甲基次黄嘌呤的 N1 配位的首例结构确证实例。基于密度泛函理论（DFT）的计算在 BP86/def2TZVP 水平上预测，金属（II）中心与中性配体 9-mhypH 中的 N7 具有最有利的相互作用（无论是动力学还是热力学），但与去质子化配体 9-mhyp-中的 N1 具有最有利的相互作用，这与实验观察到的在中性条件下或碱性处理时的优先性一致。
