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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >Triphenylphosphine oxide (L) as solvent and ligand for metallophthalocyaninates; Synthesis and structure of [{Li(L)}(2)(mu-pc)], [Li(L)(4)][Lipc] center dot solvate, [Mg(L)pc] center dot solvate, and [Zn(L)pc] center dot solvate [German]
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Triphenylphosphine oxide (L) as solvent and ligand for metallophthalocyaninates; Synthesis and structure of [{Li(L)}(2)(mu-pc)], [Li(L)(4)][Lipc] center dot solvate, [Mg(L)pc] center dot solvate, and [Zn(L)pc] center dot solvate [German]

机译:三苯膦氧化物(L)作为溶剂和金属酞菁的配体; [{Li(L)}(2)(mu-pc)],[Li(L)(4)] [Lipc]中心点溶剂化物,[Mg(L)pc]中心点溶剂化物和[ Zn(L)pc]中心点溶剂化物[德语]

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摘要

Triphenylphosphine oxide (L) coordinates to metallophthalocyaninates of Li, Mg and Zn at 300 degrees C. After purification and recrystallization in different solvents the very soluble and stable title compounds have been isolated and structurally characterized. In [{Li(L)}(2)(mu-pc)], the Li atom lies in a distorted tetragonal pyramid of four isoindole N atoms (N-i) at a distance varying between 2.163(5) and 2.301(5) Angstrom, and an O atom at 1.863(5) Angstrom. In [Li(L)(4)] . [Lipc] . S, the Li atom of the cation coordinates four O atoms in a distorted tetrahedral arrangement at a distance varying from 1.887(9) to 1.953(9) Angstrom, while the Li atom of the anion is in a quasi quadratic planar geometry of four Ni atoms (1.951(9)-1.977(9) Angstrom) with the Li atom being displaced by 0.15 Angstrom out of the (N-i)(4) plane. The structural data of the distorted tetragonal pyramidale Mg(N-i)(4)O moiety in [Mg(L)pc] and the solvates [Mg(L)pc] . S (S = CH2Cl2, thf, 2py) generally do not vary significantly: Mg-N-i/2.035(3) -2.061(3) Angstrom, Mg-O/1.955(2)-2.000(3) Angstrom. The Mg atom is displaced by ca. 0.52 Angstrom out of the (N-i)(4) plane towards the O atom and the Mg-O-P moiety is bent (ca, 153 degrees). [Zn(L)pc] . S crystallizes as a mixed crystal of equal parts of the conformer with a bent (155.1(3)degrees) and that of a quasi linear Zn-O-P moiety (174.2(3)degrees). Structural data of the Zn(N-i)(4)O moiety: (Zn-N-i)(av): 2.024/2.013 Angstrom; Zn-O: 2.050(4)/2.081(4) Angstrom; Zn-(N-i)(4): 0.40/0.33 Angstrom. In the crystal, the Mg and Zn derivates aggregate in double layers forming pairs. The pc ligands in the triclinic complexes with good overlap of the neighbouring pc ligands are in a waving conformation, while those in the monoclinic complexes with weak overlap are in a concave conformation. [References: 36]
机译:三苯膦氧化物(L)在300℃下配位为Li,Mg和Zn的金属酞菁盐。在不同溶剂中纯化和重结晶后,已分离出非常易溶且稳定的标题化合物,并对其结构进行了表征。在[{Li(L)}(2)(mu-pc)]中,Li原子位于四个异吲哚N原子(Ni)的扭曲四边形金字塔中,间距为2.163(5)和2.301(5)埃和一个在1.863(5)埃处的O原子。在[Li(L)(4)]中。 [Lipc] S,阳离子的Li原子以扭曲的四面体排列方式协调四个O原子,其距离为1.887(9)到1.953(9)埃,而阴离子的Li原子为四个Ni的准二次平面几何形状原子(1.951(9)-1.977(9)埃),其中Li原子从(Ni)(4)平面中移出0.15埃。 [Mg(L)pc]和溶剂化物[Mg(L)pc]中扭曲的四角锥Mg(N-i)(4)O部分的结构数据。 S(S = CH2Cl2,thf,2py)通常不会显着变化:Mg-N-i / 2.035(3)-2.061(3)埃,Mg-O / 1.955(2)-2.000(3)埃。 Mg原子被ca取代。 (N-i)(4)平面中朝O原子的距离为0.52埃,Mg-O-P部分弯曲(大约153度)。 [Zn(L)pc]。 S结晶为等角构形(155.1(3)度)和准线性Zn-O-P部分(174.2(3)度)等分体的混合晶体。 Zn(N-i)(4)O部分的结构数据:(Zn-N-i)(av):2.024 / 2.013埃; Zn-O:2.050(4)/2.081(4)埃; Zn-(N-i)(4):0.40 / 0.33埃。在晶体中,Mg和Zn衍生物以双层形式聚集,形成对。在三氯乙烯配合物中,与相邻pc配体重叠良好的pc配体呈波浪状,而在单斜配合物中具有较弱重叠的pc配体呈凹状。 [参考:36]

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