Nickel(II)-2,2'-dipyridylamine system. I. Synthesis and stereochemistry of the complexes
Nickel(II)-2,2'-dipyridylamine system. I. Synthesis and stereochemistry of the complexes
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镍(II)-2,2-联吡啶胺系统。
DOI：
10.1021/ic50059a007
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发表时间：
1968
影响因子：
4.6
通讯作者：
M. A. Robinson
中科院分区：
文献类型：
--
作者：
T. Hurley;M. A. Robinson
2,2 '-联吡啶胺（简称BPAH）与二价镍盐反应生成多种产物，其类型取决于金属与配体的比例和缔合阴离子的配位能力。因此，已经分离并表征了四面体[Ni (BPAH) Cl2]和八面体[Ni (BPAH) a](C104) 2和[Ni (BPAH) 2Cl2]。在这些配合物中，二吡啶胺通过两个吡啶氮以双齿方式配位。在丁醇的环境温度下，胺的去质子化导致顺磁性[Ni (BPAH) 2Cl2]物质转化为六配位聚合物材料，其通式为Ni (BPA) 2，其中去质子化的联吡啶胺部分（简称BPA）以三叉键方式配位，胺氮作为桥接。这种聚合物很容易被水、吡啶和其他络合溶剂的作用所切割。[Ni (BPA) -Cl2]在萘中高温脱质子或脱质子聚合物与氯化镍（II）反应，同样在高温下，产生红色结晶的三核配合物，分子式为[Ni3 (BPA) 4Cl2]。二（2,2′-联吡啶胺）氯化铜（II）和二（2,2′-联吡啶胺）高氯酸钯（II）的脱质子反应得到了期望的四坐标方平面产物。对钯、铜和镍的去质子配合物进行了比较，并将它们的易形成性与中心金属离子的几何形状和电子排列进行了比较。
The reaction of 2, 2'-bipyridylamine (abbreviated BPAH) with divalent nickel salts results in the formation of several products, the type of which depends on the metal: ligand ratio and the coordinating ability of the associated anion. Thus, tetrahedral [Ni (BPAH) Cl2] and octahedral [Ni (BPAH) a](C104) 2 and [Ni (BPAH) 2Cl2] have been isolated and characterized. In these complexes, dipyridylamine coordinates in a bidentate manner through the two pyridine nitrogens. Deprotonation of the amine at ambient temperature in butanol results in the conversion of the paramagnetic [Ni (BPAH) 2Cl2] species into a six-coordinate polymeric material of the general formula Ni (BPA) 2 where the deprotonated bipyridylamine moiety (ab-breviated BPA) is coordinating in a tridentate manner with the amine nitrogen acting as a bridge. This polymer is cleaved quite readily by the action of water, pyridine, and, presumably, other complexing solvents. Deprotonation of [Ni (BPAH)-Cl2] at high temperatures in naphthalene or reaction of the deprotonated polymer with nickel (II) chloride, also at high temperatures, yields a red crystalline trinuclear complex of the molecular formula [Ni3 (BPA) 4Cl2]. Deprotonation of bis (2, 2'-bipyridylamine) copper (II) chloride and bis (2, 2'-bipyridylamine) palladium (II) perchlorate give the expected fourcoordinate square-planar product. The deprotonated complexes of palladium, copper, and nickel are compared and corre-lations are made between their ease of formation and the geometry and electronic arrangement of the central metal ion.