Me2P(BH3)CH2SiMe3 | 1160717-75-8

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: Me2P(BH3)CH2SiMe3
• 英文别名: [Dimethyl(trimethylsilylmethyl)phosphaniumyl]boranuide；[dimethyl(trimethylsilylmethyl)phosphaniumyl]boranuide
• CAS: 1160717-75-8
• 化学式: C₆H₂₀BPSi
• 分子量: 162.095
• InChiKey: SIDLXHLXDXZLGI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.42
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  Me2P(BH3)CH2SiMe3 在 n-butyllithium 作用下， 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  Synthesis and structural characterisation of alkali metal complexes of heteroatom-stabilised 1,4- and 1,6-dicarbanions

  摘要：

  一种直接的彼得森烯化反应在[{(Me2PhSi)3C}Li(THF)]或原位生成的[(Me3Si)2{Ph2P(BH3)}CLi(THF)n]与聚甲醛之间进行，分别生成烯烃(Me2PhSi)2CCH2 (1)和(Me3Si){Ph2P(BH3)}CCH2 (2)，且产率良好。对1进行超声处理及在THF中与锂反应，得到锂配合物[ {(Me2PhSi)2C(CH2)}Li(THF)n]2 (3)，该产物在二乙醚中与1当量的KOBut反应，生成钾盐[ {(Me2PhSi)2C(CH2)}K(THF)]2 (4)。同样，2在THF中与锂进行超声处理后得到锂配合物[[{Ph2P(BH3)}(Me3Si)C(CH2)]Li(THF)3]2.2THF (5)。双(膦-硼烷)[(Me3Si){Me2(H3B)P}CH(Me2Si)(CH2)]2 (6)可通过[Me2P(BH3)CH(SiMe3)]Li与半当量的ClSiMe2CH2CH2SiMe2Cl进行回流THF反应制备。用二当量的MeLi在回流THF中对6进行金属化反应生成锂配合物[[{Me2P(BH3)}(Me3Si)C{(SiMe2)(CH2)}]Li(THF)3]2 (9)，而在冷二乙醚中用二当量的MeK进行金属化则通过再结晶得到钾配合物[[{Me2P(BH3)}(Me3Si)C{(SiMe2)(CH2)}]2K2(THF)4]∞ (10)。X射线晶体学显示，锂配合物5结晶为离子分子物种，而钾配合物4和10分别结晶为片状和链状聚合物。

  DOI：

  10.1039/b822054a
• 作为产物：
  描述：

  三甲基氯硅烷 、 trimethylphosphine-borane 在 正丁基锂 作用下， 以 四氢呋喃 、 hexanes 为溶剂， 以85%的产率得到Me2P(BH3)CH2SiMe3
  参考文献：
  名称：

  Synthesis and structural characterisation of alkali metal complexes of heteroatom-stabilised 1,4- and 1,6-dicarbanions

  摘要：

  一种直接的彼得森烯化反应在[{(Me2PhSi)3C}Li(THF)]或原位生成的[(Me3Si)2{Ph2P(BH3)}CLi(THF)n]与聚甲醛之间进行，分别生成烯烃(Me2PhSi)2CCH2 (1)和(Me3Si){Ph2P(BH3)}CCH2 (2)，且产率良好。对1进行超声处理及在THF中与锂反应，得到锂配合物[ {(Me2PhSi)2C(CH2)}Li(THF)n]2 (3)，该产物在二乙醚中与1当量的KOBut反应，生成钾盐[ {(Me2PhSi)2C(CH2)}K(THF)]2 (4)。同样，2在THF中与锂进行超声处理后得到锂配合物[[{Ph2P(BH3)}(Me3Si)C(CH2)]Li(THF)3]2.2THF (5)。双(膦-硼烷)[(Me3Si){Me2(H3B)P}CH(Me2Si)(CH2)]2 (6)可通过[Me2P(BH3)CH(SiMe3)]Li与半当量的ClSiMe2CH2CH2SiMe2Cl进行回流THF反应制备。用二当量的MeLi在回流THF中对6进行金属化反应生成锂配合物[[{Me2P(BH3)}(Me3Si)C{(SiMe2)(CH2)}]Li(THF)3]2 (9)，而在冷二乙醚中用二当量的MeK进行金属化则通过再结晶得到钾配合物[[{Me2P(BH3)}(Me3Si)C{(SiMe2)(CH2)}]2K2(THF)4]∞ (10)。X射线晶体学显示，锂配合物5结晶为离子分子物种，而钾配合物4和10分别结晶为片状和链状聚合物。

  DOI：

  10.1039/b822054a

文献信息

• A Suite of Sterically-Demanding Hybrid Alkyl/Cyclopentadienyl Ligands
  作者：Keith Izod、Claire F. Jones、Elizabeth P. Wildman、Ross W. Harrington、Paul G. Waddell

  DOI：10.1021/acs.organomet.7b00662

  日期：2017.11.13

  PhCH2K to give the dipotassium salt [(Me3Si)CPMe2(BH3)}SiMe2(C5Me4)}]K2(THF). X-ray crystallography revealed that the dipotassium salts of these hybrid ligands crystallize as zigzag polymers or three-dimensional networks. The suitability of the dipotassium salts as ligand transfer reagents for the synthesis of lanthanide complexes was probed through the synthesis of the lanthanum(III) complex [(Me3S

  杂烷基/环戊二烯基“约束几何”配体（Me 3 Si）2 CH SiMe 2（C 5 H 5）}，（Me 3 Si）2 CH SiMe 2（C 5 Me 4 H）}和（Me通过溴硅烷（Me 3 Si）2 CH（SiMe 2）反应合成了3 Si）2 CH SiMe 2（C 5 H 4 -3-SiMe 3）}Br）与相应的环戊二烯酸锂。这些配体与过量的MeK金属化可得到相应的二钾盐[（Me 3 Si）2 C SiMe 2（C 5 H 4）}] K 2（OEt 2）0.5，[（Me 3 Si）2 C SiMe 2（C 5 Me 4）}] K 2（OEt 2）和[[（Me 3 Si）2 C SiMe 2（C 5 H 3 -3-SiMe 3）}] K 2（C6 H 6）] 2 ·2C 6 H 6重结晶后。同样，膦-硼烷取代的氯硅烷（Me 3 Si）CH PMe 2（BH 3）}（SiMe
• Acyclic Dialkylstannylene and -Plumbylene Compounds That Are Monomeric in the Solid State
  作者：Keith Izod、Corinne Wills、William Clegg、Ross W. Harrington

  DOI：10.1021/om900614q

  日期：2009.10.12

  The new phosphine-borane adduct (Me2PhSi)CH2P(BH3)Me-2 is prepared by the reaction between Me2PhSiCl and in situ-gencrated Me2P(BH3)CH2Li; the adduct undergoes clean deprotonation on treatment with n-BuLi to give the phosphine-borane-stabilized carbanion complex [(Me2PhSi)-Me2P(BH3)}CH]Li. The reaction between 2 equiv of [(Me2PhSi)Me2P(BH3)}CH]Li and either CP2Sn or CP2Pb gives the acyclic dialkylstannylene and -plumbylene compounds rac-[(Me2PhSi)-Me2P(BH3))CH](2)E [E = Sn (13), Pb (14)]. Similarly, the reaction between 2 equiv Of [(Me3Si)-Me2P(BH3)}CH]Li and either CP2Sn or CP2Pb yields rac-[(Me3Si)Me2P(BH3)}CH](2)E [E = Sn (15), Pb (16)]. X-ray crystallography reveals that compounds 13-16 crystallize as discrete monomers that are stabilized by two agostic-type B-H center dot center dot center dot E contacts in each case; multielement NMR spectroscopy and UV/visible spectroscopy indicate that these agostic-type contacts are preserved in solution. DFT calculations reveal that these B-H... E contacts stabilize compounds 13-16 by between 38.0 and 43.7 kcal mol(-1). Calculations suggest that the dimerization of 15, which is isoelectronic with the archetypal dialkylstannylene (Me3Si)(2)CH}(2)Sn, to the corresponding distannene [(Me3Si)Me2P(BH3)}CH](2)Sn=Sn[CHP(BH3)Me-2}(SiMe3)](2) (15(2)) is disfavored by some 30.5 kcal mol(-1.)
• Synthesis and structural characterisation of alkali metal complexes of heteroatom-stabilised 1,4- and 1,6-dicarbanions
  作者：Keith Izod、Lyndsey J. Bowman、Corinne Wills、William Clegg、Ross W. Harrington

  DOI：10.1039/b822054a

  日期：——

  A straightforward Peterson olefination reaction between either [(Me2PhSi)3C}Li(THF)] or in situ-generated [(Me3Si)2Ph2P(BH3)}CLi(THF)n] and paraformaldehyde gives the alkenes (Me2PhSi)2CCH2 (1) and (Me3Si)Ph2P(BH3)}CCH2 (2), respectively, in good yield. Ultrasonic treatment of 1 with lithium in THF yields the lithium complex [(Me2PhSi)2C(CH2)}Li(THF)n]2 (3), which reacts in situ with one equivalent of KOBut in diethyl ether to give the potassium salt [(Me2PhSi)2C(CH2)}K(THF)]2 (4). Similarly, ultrasonic treatment of 2 with lithium in THF yields the lithium complex [[Ph2P(BH3)}(Me3Si)C(CH2)]Li(THF)3]2.2THF (5). The bis(phosphine-borane) [(Me3Si)Me2(H3B)P}CH(Me2Si)(CH2)]2 (6) may be prepared by the reaction of [Me2P(BH3)CH(SiMe3)]Li with half an equivalent of ClSiMe2CH2CH2SiMe2Cl in refluxing THF. Metalation of 6 with two equivalents of MeLi in refluxing THF yields the lithium complex [[Me2P(BH3)}(Me3Si)C(SiMe2)(CH2)}]Li(THF)3]2 (9), whereas metalation with two equivalents of MeK in cold diethyl ether yields the potassium complex [[Me2P(BH3)}(Me3Si)C(SiMe2)(CH2)}]2K2(THF)4]∞ (10) after recrystallisation. X-Ray crystallography shows that, whereas the lithium complex 5 crystallises as a discrete molecular species, the potassium complexes 4 and 10 crystallise as sheet and chain polymers, respectively.

  一种直接的彼得森烯化反应在[(Me2PhSi)3C}Li(THF)]或原位生成的[(Me3Si)2Ph2P(BH3)}CLi(THF)n]与聚甲醛之间进行，分别生成烯烃(Me2PhSi)2CCH2 (1)和(Me3Si)Ph2P(BH3)}CCH2 (2)，且产率良好。对1进行超声处理及在THF中与锂反应，得到锂配合物[ (Me2PhSi)2C(CH2)}Li(THF)n]2 (3)，该产物在二乙醚中与1当量的KOBut反应，生成钾盐[ (Me2PhSi)2C(CH2)}K(THF)]2 (4)。同样，2在THF中与锂进行超声处理后得到锂配合物[[Ph2P(BH3)}(Me3Si)C(CH2)]Li(THF)3]2.2THF (5)。双(膦-硼烷)[(Me3Si)Me2(H3B)P}CH(Me2Si)(CH2)]2 (6)可通过[Me2P(BH3)CH(SiMe3)]Li与半当量的ClSiMe2CH2CH2SiMe2Cl进行回流THF反应制备。用二当量的MeLi在回流THF中对6进行金属化反应生成锂配合物[[Me2P(BH3)}(Me3Si)C(SiMe2)(CH2)}]Li(THF)3]2 (9)，而在冷二乙醚中用二当量的MeK进行金属化则通过再结晶得到钾配合物[[Me2P(BH3)}(Me3Si)C(SiMe2)(CH2)}]2K2(THF)4]∞ (10)。X射线晶体学显示，锂配合物5结晶为离子分子物种，而钾配合物4和10分别结晶为片状和链状聚合物。