Synthesis and structural studies of binuclear platinum(II) complexes with a novel phosphorus-nitrogen-phosphorus ligand

Barloy L.; Malaise G.; Ramdeehul S.; Newton C.; Osborn JA.; Kyritsakas N.

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Synthesis and structural studies of binuclear platinum(II) complexes with a novel phosphorus-nitrogen-phosphorus ligand

机译：新型磷-氮-磷配体的双核铂（II）配合物的合成与结构研究

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The new pyridinediphosphinite ligand PONOP (1) was synthesized in one step from 2,6-pyridinedimethanol and diphenylchlorophosphane. Reaction of 1 with PtCl2(PhCN)(2) led to the neutral homobimetallic complex [Pt2Cl4-(PONOP)(2)] (2), where the benzonitriles have been substituted by the phosphorus atoms of 1. The X-ray structure of 2 revealed a metallamacrocycle where the pyridines remained free. Addition of 2 equiv of [Cu(MeCN)(4)](BF4) to 2 led to CuCl and to the binuclear dicationic complex [Pt2Cl2(PONOP)(2)](BF4)(2) (3), where chloro ligands have been substituted by pyridine groups. Conversely, reaction of 3 with chloride anions gave back complex 2. Solid-state (X-ray) and solution (NMR) studies indicated that after the transformation of 2 into 3, the platinum centers were brought much closer and the pyridinediphosphinite ligand was stiffened. The methylene NMR protons of 3 were strongly deshielded, and the corresponding proton-phosphorus coupling constants followed a Karplus-type relationship. [References: 40]

机译：新的吡啶二亚膦酸酯配体PONOP（1）是由2,6-吡啶二甲醇和二苯基氯膦一步一步合成的。 1与PtCl2（PhCN）（2）的反应生成中性均双金属配合物[Pt2Cl4-（PONOP）（2）]（2），其中苯甲腈已被1的磷原子取代。X射线结构图2显示了金属lamcrocrocycle，其中吡啶保持游离。将2当量的[Cu（MeCN）（4）]（BF4）添加到2中会生成CuCl和双核双键型络合物[Pt2Cl2（PONOP）（2）]（BF4）（2）（3），其中有氯配体已被吡啶基取代。相反，3与氯离子的反应生成了络合物2。固态（X射线）和溶液（NMR）研究表明，在2转化为3后，铂中心更加紧密，吡啶二亚膦酸酯配体变硬。 3的亚甲基NMR质子被强去屏蔽，相应的质子-磷偶联常数遵循Karplus型关系。 [参考：40]

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《Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics》 |2003年第9期|共6页
作者
Barloy L.; Malaise G.; Ramdeehul S.; Newton C.; Osborn JA.; Kyritsakas N.;
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正文语种 eng
中图分类化学;
关键词
Coordination chemistry; Palladium(ii); Construction; Copper(i); Reactivity; Catalysis;

机译：配位化学;钯（ii）;结构;铜（i）;反应性;催化;

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1. Synthesis and structural studies of binuclear platinum(II) complexes with a novel phosphorus-nitrogen-phosphorus ligand [J] . Barloy L., Malaise G., Ramdeehul S., Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics . 2003,第9期

机译：新型磷-氮-磷配体的双核铂（II）配合物的合成与结构研究
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Synthesis and structural studies of binuclear platinum(II) complexes with a novel phosphorus-nitrogen-phosphorus ligand

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