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首页> 外文期刊>Acta Crystallographica Section E: Crystallographic Communications >Crystal structures of a novel NNN pincer ligand and its dinuclear titanium(IV) alkoxide pincer complex
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Crystal structures of a novel NNN pincer ligand and its dinuclear titanium(IV) alkoxide pincer complex

机译：新型NNN钳形配体的晶体结构及其双核钛醇盐钳形配合物

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摘要

This report describes a synthetic protocols and the crystal structures involving a novel pincer-type H3[NNN] ligand, namely di-μ-bromido-μ-{2-(2,2-di­methylpropanimido­yl)-N-[2-(2,2-di­methyl­propanimido­yl)-4-methyl­phen­yl]-4-methylaniline}-bis­[(diethyl ether)lithium], [Li2Br2(C24H33N3)(C4H10O)2] (1) and a dinuclear metal complex, namely di-μ-bromido-2:3κ4Br:Br-bis­{2-(2,2-di­methylpropanimido­yl)-N-[2-(2,2-di­methyl­propanimido­yl)-4-methyl­phen­yl]-4-methylaniline}-1κ3N,N′,N′′;4κ3N,N′,N′′-tetra-μ-iso­propano­lato-1:2κ4O:O;3:4κ4O:O-diiso­propano­lato-1κO,4κO-2,3-dilithium-1,4-dititanium, [Li2Ti2Br2(C24H32N3)2(C3H7O)6] or {[NHNNH]Ti(OiPr)3(LiBr)2}2 (2). Complex 1, which sits on a twofold rotation axis, is a rare example of a pincer-type ligand which bears ketimine side arms. A unique feature of complex 1 is that the ketimine N atoms have an LiBr(Et2O) fragment bonded to them, with the Li atom adopting a distorted tetra­hedral geometry. This particular fragment creates an LiBr bridge between the two ketimine sidearms, which leads to a cage-type appearance of the ligand. Complex 2 consists of the previously described ligand and a TiIV metal atom in an octa­hedral environment, and is located on an inversion center. Complex 2 crystallizes as a dinuclear species with the metal atoms being bridged by an LiBr entity [the Br atoms are disordered and refined in two positions with their site occupation factors refining to 0.674 (12)/0.372 (12)], and the Li cation being bonded to the isopropoxide O atoms (Li having a tetra­hedral coordination as in 1). The organic ligand of compound 2 exhibits disorder in its periphery groups; isopropyl and tert-butyl groups (occupation factors fixed at 0.6/0.4). The novel [NNN]H3 pincer-type ligand was characterized by multinuclear and multidimensional NMR, HRMS and X-ray crystallography. The dinuclear metal complex 2 was characterized by X-ray crystallography. Although each structure exhibits donor N—H groups, no hydrogen bonding is found in either one, perhaps due to the bulky groups around them. One of the ethyl groups of the ether ligand of 1 is disordered and refined in two parts with site-occupation factors of 0.812 (8) and 0.188 (8). One and a half toluene solvent mol­ecules are also present in the asymmetric unit of 2. The toluene mol­ecules were significantly disordered and could not be modeled properly, thus SQUEEZE [Spek (2015). Acta Cryst. C71, 9–18] was used to remove their contributions to the overall intensity data.
机译：该报告介绍了一种合成方案，以及涉及一种新型钳型H3 [NNN]配体的晶体结构，即二μ-溴代-μ-{2-（2,2-二甲基丙酰胺基）-N- [2-（2， 2-二甲基丙酰胺基）-4-甲基苯基] -4-甲基苯胺}-双[（二乙醚）锂]，[Li2Br2（C24H33N3）（C4H10O）2]（1）和双核金属络​​合物，即di-bromido- 2：3κ4Br：Br-双{2-（2,2-二甲基丙酰胺基）-N- [2-（2,2-二甲基丙酰胺基）-4-甲基苯基] -4-甲基苯胺}-1κ3N，N'，N''; 4κ3N，N'，N''-四-μ-异丙醇-1：2κ4O：O; 3：4κ4O：O-二异丙醇-1KO，4κO-2,3-二锂-1,4-二钛，[Li2Ti2Br2（C24H32N3） 2（C3H7O）6]或{[NHNNH] Ti（OiPr）3（LiBr）2} 2（2）。位于两倍旋转轴上的复合物1是带有ketimine侧臂的钳型配体的罕见实例。配合物1的独特之处在于，酮亚胺N原子具有与其键合的LiBr（Et2O）片段，而Li原子采用扭曲的四面体几何形状。这个特定的片段在两个酮亚胺侧臂之间形成一个LiBr桥，导致配体呈笼状出现。络合物2在八面体环境中由前述配体和TiIV金属原子组成，并且位于反转中心。配合物2结晶为双核物种，其中金属原子被LiBr实体桥接[Br原子在两个位置无序和精炼，其位点占据因子精炼为0.674（12）/0.372（12）]和Li阳离子与异丙氧基O原子（如1中具有四面体配位的Li）键合。化合物2的有机配体在其外围基团中表现出无序性。异丙基和叔丁基（占用因子固定为0.6 / 0.4）。新型[NNN] H3钳型配体通过多核和多维NMR，HRMS和X射线晶体学表征。双核金属络​​合物2通过X射线晶体学表征。尽管每个结构均显示供体NH基团，但在两个结构中均未发现氢键，可能是由于其周围的基团庞大。 1的醚配体的一个乙基基团被无序地分为两部分，其位置占据因子分别为0.812（8）和0.188（8）。在2的不对称单元中也存在一个半甲苯溶剂分子。甲苯分子明显无序，无法正确建模，因此受到挤压[Spek（2015）。 Acta Cryst。 C71，9–18]用于删除它们对总体强度数据的贡献。

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