三（1,2 - 二甲氧基乙烷 - O,O'）钡双（2,2,5,5 - 四甲基 - 2,5 - 二硅磷杂环戊烷）的合成以及甲苯溶液中的单体 - 二聚体平衡

Synthesis of Tris(1,2-dimethoxyethane-O,O')barium Bis(2,2,5,5-tetramethyl-2,5-disilaphospholanide) and the Monomer-Dimer Equilibrium in Toluene Solution.

作者信息

Westerhausen M., Hartmann M., Schwarz W.

机构信息

Institut für Anorganische Chemie der Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany.

出版信息

Inorg Chem. 1996 Apr 24;35(9):2421-2426. doi: 10.1021/ic950854y.

DOI:10.1021/ic950854y

PMID:11666451

Abstract

(1,2-Dimethoxyethane-O,O')lithium phosphanide (dme)LiPH(2) reacts with 1,2-bis(chloro-dimethylsilyl)ethane to give 2,2,5,5-tetramethyl-2,5-disilaphospholane, 1, as well as 1,1,4,4-tetramethyl-1,4-bis(2,2,5,5-tetramethyl-2,5-disilaphospholanyl)-1,4-disilabutane, 2 (P(2)Si(6)C(18)H(48), space group P&onemacr;, a = 943.3(2) pm, b = 1278.3(3) pm, c = 1413.3(2) pm, alpha = 72.45(1) degrees, beta = 78.13(1) degrees, gamma = 70.83(1) degrees, d = 1.081 g cm(-)(3), Z = 2, wR2 = 0.1553 at 6548 F(2) values). The reaction of 2,2,5,5-tetramethyl-2,5-disilaphospholane 1 and barium bis[bis(trimethylsilyl)amide] in 1,2-dimethoxyethane yields nearly quantitatively tris(1,2-dimethoxyethane-O,O')barium bis(2,2,5,5-tetramethyl-2,5-disilaphospholanide), 3A, which crystallizes in the monoclinic space group C2/c (BaP(2)Si(4)O(6)C(24)H(62), a = 2152.3(1) pm, b = 1381.5(1) pm, c = 1459.7(1) pm, beta = 113.73(1) degrees, d(calc) = 1.268 g cm(-)(3), Z = 4, wR2 = 0.0989 at 5220 F(2) values). Due to the high coordination number of eight of the barium center, rather long Ba-P distances of 333 pm are observed. With loss of the complexating ether solvent this compound forms a dimer 3B of the type R(dme)Ba(&mgr;-R)(3)Ba(dme)(2) in toluene or benzene solution as can be proven by (31)P{(1)H}-NMR spectroscopy ((2)J(P-P) = 6.7 Hz) and by X-ray structure analysis (Ba(2)P(4)Si(8)O(6)C(48)H(106), space group P2(1)/n, a = 1256.3(2) pm, b = 2000.0(3) pm, c = 2986.9(2) pm, beta = 98.929(9) degrees, d(calc) = 1.257 g cm(-)(3), Z = 4, wR2 = 0.1334 at 11580 F(2) values). The Ba-P bond lengths vary between 318 and 338 pm.

摘要

（1,2 - 二甲氧基乙烷 - O,O'）磷化锂（dme）LiPH₂与1,2 - 双（氯 - 二甲基甲硅烷基）乙烷反应生成2,2,5,5 - 四甲基 - 2,5 - 二硅磷杂环戊烷（1）以及1,1,4,4 - 四甲基 - 1,4 - 双（2,2,5,5 - 四甲基 - 2,5 - 二硅磷杂环戊烷基） - 1,4 - 二硅丁烷（2）（P₂Si₆C₁₈H₄₈，空间群P&onemacr;，a = 943.3(2) pm，b = 1278.3(3) pm，c = 1413.3(2) pm，α = 72.45(1)°，β = 78.13(1)°，γ = 70.83(1)°，d = 1.081 g cm⁻³，Z = 2，在6548个F₂值下wR₂ = 0.1553）。2,2,5,5 - 四甲基 - 2,5 - 二硅磷杂环戊烷（1）与双[双（三甲基甲硅烷基）酰胺]钡在1,2 - 二甲氧基乙烷中反应几乎定量生成三（1,2 - 二甲氧基乙烷 - O,O'）钡双（2,2,5,5 - 四甲基 - 2,5 - 二硅磷杂环戊烷化物）（3A），其在单斜空间群C2/c中结晶（BaP₂Si₄O₆C₂₄H₆₂，a = 2152.3(1) pm，b = 1381.5(1) pm，c = 1459.7(1) pm，β = 113.73(1)°，d(calc) = 1.268 g cm⁻³，Z = 4，在5220个F₂值下wR₂ = 0.0989）。由于钡中心的高配位数为8，观察到Ba - P距离相当长，为333 pm。随着络合醚溶剂的损失，该化合物在甲苯或苯溶液中形成R(dme)Ba(μ - R)₃Ba(dme)₂型二聚体（3B），这可通过³¹P{(¹H)}-NMR光谱（²J(P-P) = 6.7 Hz）和X射线结构分析得到证明（Ba₂P₄Si₈O₆C₄₈H₁₀₆，空间群P2(1)/n，a = 1256.3(2) pm, b = 2000.0(3) pm, c = 2986.9(2) pm, β = 98.929(9)°，d(calc) = 1.257 g cm⁻³，Z = 4，在11580个F₂值下wR₂ = 0.1334）。Ba - P键长在318至338 pm之间变化。