Phosphine analogs of cisplatin. Synthesis and x-ray structure of bis(.mu.-hydroxo)bis(bis(trimethylphosphine) platinum(II) dinitrate and its reactivity with 1-methylcytosine. X-ray structure of bis(.mu.-1-methylcytosinato-N3,N4)bis(bis(trimethylphosphine)platinum(II) dinitrate
Phosphine analogs of cisplatin. Synthesis and x-ray structure of bis(.mu.-hydroxo)bis(bis(trimethylphosphine) platinum(II) dinitrate and its reactivity with 1-methylcytosine. X-ray structure of bis(.mu.-1-methylcytosinato-N3,N4)bis(bis(trimethylphosphine)platinum(II) dinitrate
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顺铂的膦类似物。
DOI：
10.1021/ic00348a008
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发表时间：
1990
影响因子：
4.6
通讯作者：
B. Longato
中科院分区：
文献类型：
--
作者：
G. Trovo;G. Bandoli;U. Casellato;B. Corain;M. Nicolini;B. Longato
990年3月27日，合成了配合物4-[(？)3)2(µ-0)]2(03)2，并用多核、~(31)P和~(95)P核磁共振谱对其进行了表征。单晶X-射线分析证实了溶液中阳离子络合物的二聚性。该化合物属单斜晶系，空间群为P2Jn，晶胞参数为a=15.511(7)α，b=12.315(5)α，c=6.964(4)A，ç=97.67(4)，Z=2。用重原子方法求解结构，用最小二乘法修正R=0.048，得到2748个唯一数据(I>；3(/))。阳离子单元di-[(PMe3)2Pt(u-OH)]22+以扭曲的方形平面构型与铂原子桥联。P-铂-P和O-铂-O角分别为95.4(1)和75.9(4)。P4Pt202的骨架是平面的，O-O距离较短(2.54(1)A)。用3IP核磁共振波谱研究了该配合物与1-甲基胞嘧啶(1-MeCy)在H_20和二甲基亚砜(DMSO)中的反应。在室温下，顺式-[(？)3)_2(µ-)]_(22+)与碱基反应数小时，环外氨基脱质子，胞嘧啶配位。主要反应产物为双核配合物>；-[(？)3)2(µ-L-MeCy(-H))]2(N03)2，用多核核磁共振波谱和单晶X-射线分析对其进行了表征。该配合物属三斜晶系，空间群为PI，晶胞参数为a=10.320(4)k，b=10.431(5)A，c=17.426(8)A，a=92.39(4)，？=99.13(4)，y=94.54(5)，Z=2。两个去质子化的1-MeCy分子以N3，N4的方式连接了两个m-(PMe3)2Pt基团，形成了一个双核物种，其中两个金属原子的配位面形成了46.2的二面角。在80℃，在H20或DMSO溶液中，该络合物解离成相应的单核物种。参照胺类化合物的分子结构和溶液状态，讨论了所制备的配合物的分子结构和溶液状态。
March 27,¡ 990 The complex 4-[(ß3) 2 (µ-0)] 2 (03) 2 has beenprepared and characterized by multinuclear, 31P, and, 95Pt NMR spectroscopy. The dimeric nature of the cationic complex found in solution has been confirmed in the solid state by single-crystal X-ray analysis. The compound crystallizes in the monoclinic system, space group P2Jn, with a= 15.511 (7) Á, b= 12.315 (5) Á, c= 6.964 (4) A, ß= 97.67 (4), and Z= 2. The structure was solved by heavy-atom methods and refined by least-squares techniques to R= 0.048 for 2748 unique data (I> 3 (/)). The cationic unit di-[(PMe3) 2Pt (u-OH)] 22+ contains bridging hydroxo ligands with the Pt atoms in a distorted square-planar geometry. The P-Pt-P and O-Pt-O angles are 95.4 (1) and 75.9 (4), respectively. The P4Pt202 skeleton is planar with a rather short O---O distance (2.54 (1) A). The reaction of this complex with 1-methylcytosine (1-MeCy) has been investigated, in H20 and dimethyl sulfoxide (DMSO), by 3IP NMR spectroscopy, cis-[(ß3) 2 (µ-)] 22+ reacts with thenucleobase, at room temperature in a few hours, with deprotonation of the exocyclic amino group and metal coordination of the cytosinate ligand. The main reaction product is the dinuclear complex>-[(ß3) 2 (µ-l-MeCy (-H))] 2 (N03) 2, which has been characterized in solution by multinuclear NMR spectroscopy and in the solid state by single-crystal X-ray analysis. The complex crystallizes in the triclinic system, space group Pi, with a= 10.320 (4) k, b= 10.431 (5) A, c= 17.426 (8) A, a= 92.39 (4), ß= 99.13 (4), y= 94.54 (5), and Z= 2. The structure was solved by heavy-atom methods and refined to R= 0.038 for 5900 unique data (I> 3 (/)). The two deprotonated 1-MeCy molecules bridge two m-(PMe3) 2Pt moieties in a N3, N4 head-to-tail fashion to form a dinuclear species in which the coordination planes of the two metal atoms form a dihedral angle of 46.2. At 80 C, in H20 or DMSO solution, the complex dissociates to the corresponding mononuclear species. The molecular structures and the solution state of the prepared complexes are discussed with reference to those of the amine analogues.