[(tri-n-butylphosphine)Ag]2(oxalate) | 864666-77-3

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: [(tri-n-butylphosphine)Ag]2(oxalate)
• 英文别名: [nBu3PAg(ox)AgPBu3n]
• CAS: 864666-77-3
• 化学式: C₂₆H₅₄Ag₂O₄P₂
• 分子量: 708.396
• InChiKey: NHANJUIPNFQTLR-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
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• 拓扑面积：
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• 氢给体数：
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• 氢受体数：
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反应信息

• 作为反应物：
  描述：

  [(tri-n-butylphosphine)Ag]2(oxalate) 以 neat (no solvent, solid phase) 为溶剂， 生成 银
  参考文献：
  名称：

  Tri-n-Butyl-Phosphan-Silber(I)-Komplexe mit Carboxylat-, Troponolat- bzw. N-Hydroxyphthalimid-Teilstrukturen; Synthese und Verwendung als Spin-On-Precursoren

  摘要：

  AbstractTri‐n‐Butyl‐Phosphane Silver(I) Complexes with Carboxylate‐, Tropolonate‐ or N‐Hydroxyphthalimide Building Blocks; Synthesis and their Use as Spin‐on PrecursorsTreatment of AgNO3 (1) with one equivalent of HX (2a, X = trop; 2b, X = phthal; trop = troponolate; phthal = N‐hydroxy‐phthalimide anion) in presence of NEt3 affords the silver(I) salts [AgX] (3a, X = trop; 3b, X = phthal) in quantitative yield. When instead of 2a and 2b oxalic acid (4a) or quadratic acid (1,2‐dihydroxycyclobutene‐3,4‐dione) (4b) are reacted with 1 under similar reaction conditions, then the corresponding disilver salts [Ag2E] (5a, E = ox; 5b, E = quad; ox = oxalate; quad = quadratic acid dianion) are accessible in excellent yield.The reaction of 3 and 5 with m equivalents of nBu3P (6) produces the phosphane silver(I) complexes (nBu3P)mAgX (m = 1: 7a, X = trop; 7b, X = phthal; m = 2: 8a, X = trop; 8b, X = phthal) and (nBu3P)mAg‐E‐Ag(PnBu3)m (m = 1: 9a, E = ox; 9b, E = quad; m = 2: 10a, E = ox; 10b, E = quad; m = 3: 11a, E = ox; 11b, E = quad), which can be isolated after appropriate work‐up as colourless (9–11), yellow (7a, 8a) or red‐purple (7b, 8b) species.The solid‐state structures of 7b and 9a are reported. Complex 7b exists of two (nBu3P)Ag(phthal) units in which the oxygen atoms of the N‐hydroxyphthalimide anions are μ‐bridging both silver atoms. The thus formed 4‐membered Ag2O2 cycle is planar and the silver atoms show the coordination number 3. Complex 9a exhibits a planar dinuclear structure with the anticipated oxalate building block in a μ‐1,2,3,4 bridging mode. As typical for 7b also for 9a a tricoordinated silver(I) ion is present, whereby the phosphanes act as neutral capping ligands.The thermal behaviour of selected species (7b, 8b, 9a, 10a, 11a and 11b) was studied by applying thermogravimetry. The decomposition of the latter complexes starts between 100–160 °C and is completed in the region of 350–400 °C. One – four decomposition steps are typical. The decomposition of 9a was studied in detail. Elimination of nBu3P occurs at first, while loss of CO2 from in‐situ generated [Ag2ox] gives elemental silver. For that reason, 9a was used as spin‐on precursor in the deposition of silver on TiN‐coated oxidized silicon wafers. REM studies showed that closed and homogeneous silver layers were formed. The resistivity was determined to 3.4 μΩcm.

  DOI：

  10.1002/zaac.200400510
• 作为产物：
  描述：

  三丁基膦 、 silver oxalate 以 乙醚 为溶剂， 以97%的产率得到[(tri-n-butylphosphine)Ag]2(oxalate)
  参考文献：
  名称：

  Tri-n-Butyl-Phosphan-Silber(I)-Komplexe mit Carboxylat-, Troponolat- bzw. N-Hydroxyphthalimid-Teilstrukturen; Synthese und Verwendung als Spin-On-Precursoren

  摘要：

  AbstractTri‐n‐Butyl‐Phosphane Silver(I) Complexes with Carboxylate‐, Tropolonate‐ or N‐Hydroxyphthalimide Building Blocks; Synthesis and their Use as Spin‐on PrecursorsTreatment of AgNO3 (1) with one equivalent of HX (2a, X = trop; 2b, X = phthal; trop = troponolate; phthal = N‐hydroxy‐phthalimide anion) in presence of NEt3 affords the silver(I) salts [AgX] (3a, X = trop; 3b, X = phthal) in quantitative yield. When instead of 2a and 2b oxalic acid (4a) or quadratic acid (1,2‐dihydroxycyclobutene‐3,4‐dione) (4b) are reacted with 1 under similar reaction conditions, then the corresponding disilver salts [Ag2E] (5a, E = ox; 5b, E = quad; ox = oxalate; quad = quadratic acid dianion) are accessible in excellent yield.The reaction of 3 and 5 with m equivalents of nBu3P (6) produces the phosphane silver(I) complexes (nBu3P)mAgX (m = 1: 7a, X = trop; 7b, X = phthal; m = 2: 8a, X = trop; 8b, X = phthal) and (nBu3P)mAg‐E‐Ag(PnBu3)m (m = 1: 9a, E = ox; 9b, E = quad; m = 2: 10a, E = ox; 10b, E = quad; m = 3: 11a, E = ox; 11b, E = quad), which can be isolated after appropriate work‐up as colourless (9–11), yellow (7a, 8a) or red‐purple (7b, 8b) species.The solid‐state structures of 7b and 9a are reported. Complex 7b exists of two (nBu3P)Ag(phthal) units in which the oxygen atoms of the N‐hydroxyphthalimide anions are μ‐bridging both silver atoms. The thus formed 4‐membered Ag2O2 cycle is planar and the silver atoms show the coordination number 3. Complex 9a exhibits a planar dinuclear structure with the anticipated oxalate building block in a μ‐1,2,3,4 bridging mode. As typical for 7b also for 9a a tricoordinated silver(I) ion is present, whereby the phosphanes act as neutral capping ligands.The thermal behaviour of selected species (7b, 8b, 9a, 10a, 11a and 11b) was studied by applying thermogravimetry. The decomposition of the latter complexes starts between 100–160 °C and is completed in the region of 350–400 °C. One – four decomposition steps are typical. The decomposition of 9a was studied in detail. Elimination of nBu3P occurs at first, while loss of CO2 from in‐situ generated [Ag2ox] gives elemental silver. For that reason, 9a was used as spin‐on precursor in the deposition of silver on TiN‐coated oxidized silicon wafers. REM studies showed that closed and homogeneous silver layers were formed. The resistivity was determined to 3.4 μΩcm.

  DOI：

  10.1002/zaac.200400510