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首页> 外文期刊>Zeitschrift fur Anorganische und Allgemeine Chemie >Acyl- and Alkylidenephosphanes. XXXV. Bis[N-(trimethylsilyl)iminobenzoyl]phosphanides of Lithium and Zinc - Syntheses as well as NMR Spectroscopic, Structural, and Quantumchemical Studies
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Acyl- and Alkylidenephosphanes. XXXV. Bis[N-(trimethylsilyl)iminobenzoyl]phosphanides of Lithium and Zinc - Syntheses as well as NMR Spectroscopic, Structural, and Quantumchemical Studies

机译：酰基和亚烷基膦。 XXXV。锂和锌的双[N-（三甲基甲硅烷基）亚氨基苯甲酰基]膦酸酯-合成以及NMR光谱，结构和量子化学研究

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摘要

From the reaction of bis(tetrahydrofuran)lithium bis(trimethylsilyl)phosphanide with two equivalents of benzonitrile in 1,2-dimethoxyethane, the yellow dme complex (2a) of lithium bis[N-(trimethylsilyl)]iminobenzoyl]phosphanide (2) was obtained in 69% yield. However, the intermediate [1-[N-lithium-N-(trimethylsilyl)amido]benzylidene]trimethylsilylphosphane (1), formed by an analogous 1:1 addition in diethyl ether, turned out to be unstable and as a consequence could be characterized by nmr spectroscopic methods only; attempts to isolate the compound failed, but small amounts of the neutral complex 2b, with the ligands benzonitrile and tetrahydrofuran coordinated to lithium, precipitated. The reaction of compound 2 with zinc(II) chloride in diethyl ether gives the orange-red spiro-complex zinc bis{bis[N-(trimethylsilyl)iminobenzoyl]phosphanide} (3); this complex is also formed from bis[N-(trimethylsilyl)iminobenzoyl]phosphane (4), easily amenable by a lithium hydrogen exchange of 2 a with trifluoroacetic acid [18], and zinc bis[bis(trimethylsilyl)amide]. As derived from nmr spectroscopic studies and x-ray structure determinations, compounds 2 a {#delta#~(31)P + 63.3 ppm; P2_1; Z = 4; R_1 = 0.067}, 2 b {#delta#~(31)P + 63.3 ppm; P2_1/c; Z = 4; R_1 = 0.063}, 3 {#delta#~(31)P + 58.2 ppm, C2/c; Z = 4; R_1 = 0.037} and 4 {#delta#~(31)P + 58.1 pp, [18]} exist as cyclic 3-imino-2#lambda#~3 #sigma#~2-phosphapropenylamides and -propenylamine, respectively, in solution as well as in the solid state. Unlike hydrogen derivative 4 the bis[N-(trimethylsilyl)iminobenzoyl]phosphanide fragments N,N"-coordinating either a lithium or a zinc cation ae characterized by almost completely equalized bond lengths; typical mean distances and anlges are: P - C 180.3 and 178.7; C - N 130.5 and 131.8; N-Si 175.3 and 179.3; N-Li 202.3; N-Zn 203.5 pm; C - P - C 108.8 deg; P - C - N 130.9 deg and 132.9 deg; C - N -Li 113.0 deg, C - N -Zn 117.4 deg; N - Li-N 104.6 deg; N-Zn-N 108.8 deg. Alterations in the shape of the six membered chelate rings, caused by an exchange of the 3-imino-2#lambda#~3 #sigma#~2-phosphapropenylamide or related 2#lambda#~3 #sigma#~2-phospha-1,3-dionate units for the corresponding phosphorus free ligands, are discussed in detail. The results of quantumchemical DFT-B3LYP calculations coincide very well with the experimentally obtained findings.
机译：由双（四氢呋喃）锂双（三甲基甲硅烷基）膦化物与两当量的苄腈在1,2-二甲氧基乙烷中的反应，得到双[N-（三甲基甲硅烷基）]亚氨基苯甲酰基]膦酸锂（2）的黄色dme配合物（2a）为得到69％的产率。但是，中间体[1- [N-锂-N-（三甲基甲硅烷基）酰胺基]亚苄基]三甲基甲硅烷基膦（1）是不稳定的，因此在乙醚中以1：1的比例添加，结果不稳定。仅通过核磁共振光谱法;试图分离该化合物的尝试失败了，但沉淀了少量配体苄腈和四氢呋喃与锂配位的中性络合物2b。化合物2与氯化锌（Ⅱ）在乙醚中的反应得到橙红色螺旋络合物双{双[N [（N-（三甲基甲硅烷基）亚氨基苯甲酰基]正膦酸] zinc}（3）;该络合物也由双[N-（三甲基甲硅烷基）亚氨基苯甲酰基]膦（4）形成，很容易通过2a与三氟乙酸[18]的锂氢交换和双[双（双（三甲基甲硅烷基）酰胺]锌形成。从核磁共振光谱研究和X射线结构测定得出，化合物2 a {＃delta＃〜（31）P + 63.3 ppm; P2_1 / n; Z = 4; R_1 = 0.067}，2 b {＃delta＃〜（31）P + 63.3 ppm; P2_1 / c; Z = 4; R_1 = 0.063}，3 {＃δ＃〜（31）P + 58.2 ppm，C2 / c; Z = 4; R_1 = 0.037}和4 {＃delta＃〜（31）P + 58.1 pp，[18]}作为环状3-亚氨基-2＃lambda＃〜3＃sigma＃〜2-磷丙烯酰胺和-丙烯胺存在。溶液以及固态。与氢衍生物4不同，双[N-（三甲基甲硅烷基）亚氨基苯甲酰基]膦酸酯片段N，N“-配成锂或锌阳离子，其特征是键长几乎完全相等;典型的平均距离和阿尔格数为：P C 180.3和178.7; C-N 130.5和131.8; N-Si 175.3和179.3; N-Li 202.3; N-Zn 203.5 pm; C-P-C 108.8度; P-C-N 130.9度和132.9度; C-N- Li 113.0度，C-N -Zn 117.4度; N-Li-N 104.6度; N-Zn-N 108.8度，由三亚氨基2的交换引起的六元螯合环形状的变化详细讨论了相应的无磷配体的＃lambda＃〜3＃sigma＃〜2-磷丙烯酰胺或相关的2＃lambda＃〜3＃sigma＃〜2-phospha-1,3-二酸酯单元。 DFT-B3LYP计算与实验获得的结果非常吻合。

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