[CH₂(PPh₂=NSiMe₃)(PPh₂=S)] | 1176846-71-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: [CH₂(PPh₂=NSiMe₃)(PPh₂=S)]
• 英文别名: [CH2(PPh2=NSiMe3)(PPh2=S)]；Diphenylphosphinothioylmethyl-diphenyl-trimethylsilylimino-lambda5-phosphane；diphenylphosphinothioylmethyl-diphenyl-trimethylsilylimino-λ5-phosphane
• CAS: 1176846-71-1
• 化学式: C₂₈H₃₁NP₂SSi
• 分子量: 503.66
• InChiKey: LWDXYBOEXWSCAV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.76
• 重原子数：
  33
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  44.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [CH₂(PPh₂=NSiMe₃)(PPh₂=S)] 在 二丁基镁 作用下， 以 正庚烷 、 甲苯 为溶剂， 反应 15.0h， 以65.4%的产率得到[(PPh2=NSiMe3)(PPh2=S)CMg]2
  参考文献：
  名称：

  Synthesis and Characterization of Magnesium and Aluminum Bis(phosphoranyl)methanediide Complexes

  摘要：

  The reaction of [CH2(PPh2=NSiMe3)(PPh2=E)] (E = S (1), NSiMe3 (2)) with Mg(Bu-II)(2) in refluxing toluene afforded the magnesium bis(phosphoranyl)methanediide complexes [{(PPh2=NSiMe3)(PPh2=E)}CMg](2) (E = S (3), NSiMe3 (4)), respectively. The X-ray structures and DFT calculations of 3 and 4 show that they are bimetallic methanediide complexes of magnesium containing a strong Mg-C-methanediide electrostatic bonding. Treatment of 4 with water in toluene gave 2 and the magnesium hydroxide complex [HC(PPh2=NSiMe3)(2)Mg(mu-OH)](2) (5), confirmed by X-ray crystallography. The reaction of I with AlMe3 in refluxing toluene afforded the aluminum bis(phosphoranyl)methanediide complex [{(PPh2=NSiMe3)(PPh2=S)}CAIMe](2) (6). The X-ray structure of 6 shows that a methanediide carbon is bonded to one aluminum atom. DFT calculations of 6 demonstrate that Al-C-methanediide is highly polar with weak covalent bonding, consistent with the topological analysis of electron densities of 6.

  DOI：

  10.1021/om900985f

文献信息

• Oxo-Bridged Bis(group 4 metal unsymmetric phosphonium-stabilized carbene) Complexes
  作者：Jia-Yi Guo、Yuk-Chi Chan、Yongxin Li、Rakesh Ganguly、Cheuk-Wai So

  DOI：10.1021/om5012962

  日期：2015.4.13

  The synthesis and reactivity of oxo-bridged bis(group 4 metal unsymmetric phosphonium-stabilized carbene) complexes are described. The reaction of [CH2RNRS] (1; RN = PPh2NSiMe3, RS = PPh2S) with 1 equiv of [M(NMe2)4] (M = Zr, Hf) afforded the group 4 metal unsymmetric phosphonium-stabilized carbene complexes [M(NMe2)2(CRNRS)] (M = Zr (4), Hf (5)). Their reactions with water in toluene afforded the

  描述了羰基桥联的双（4族金属非对称phospho稳定的卡宾）配合物的合成和反应活性。[CH 2 R N R S ]（1； R N = PPh 2 NSiMe 3，R S = PPh 2 S）与1当量的[M（NMe 2）4 ]（M = Zr，Hf）反应得到第4组金属非对称phospho稳定的卡宾配合物[M（NMe 2）2（CR N R S）]（M = Zr（4），Hf（5））。他们与水在甲苯中的反应提供了羰基桥联的衍生物O [M（NMe 2）（CR N R S）] 2（M = Zr（6），Hf（7））。化合物6与AdNCO进行插入反应以形成O [Zr OC（NMe 2）NAd}（CR N R S）] 2（8； Ad ＝金刚烷基）。化合物4 - 8由NMR光谱和X-射线晶体学进行了表征。
• Synthesis and characterization of a tin(ii) bis(phosphinoyl)methanediide complex: a stannavinylidene derivative
  作者：Jiayi Guo、Kai-Chung Lau、Hong-Wei Xi、Kok Hwa Lim、Cheuk-Wai So

  DOI：10.1039/b922377k

  日期：——

  The reaction of [CH(2)(PPh(2)=NSiMe(3))(PPh(2)=S)] (1) with two equivalents of [SnN(SiMe(3))(2)}(2)] in refluxing toluene afforded novel tin(II) bis(phosphinoyl)methanediide complex 3. The structure of compound 3 has been determined by X-ray crystallography and DFT calculations. The topological analysis of the electron densities of compound 3 was performed.

  [CH（2）（PPh（2）= NSiMe（3））（PPh（2）= S）]（1）与两当量的[Sn N（SiMe（3））（2）}（ 2）]在回流的甲苯中得到新型的锡（II）双（膦酰基）甲烷二酰亚胺络合物3。化合物3的结构已经通过X射线晶体学和DFT计算确定。对化合物3的电子密度进行拓扑分析。
• (Iminophosphoranyl)(thiophosphoranyl)methanide {CH(PPh₂NSiMe₃)(Ph₂PS)}⁻ as a Ligand in Rare-Earth-Element Chemistry
  作者：Balasubramanian Murugesapandian、Magdalena Kuzdrowska、Michael T. Gamer、Larissa Hartenstein、Peter W. Roesky

  DOI：10.1021/om400001e

  日期：2013.3.11

  The (iminophosphoranyl)(thiophosphoranyl)methanide CH(PPh2═NSiMe3)(PPh2═S)}− has been introduced as a ligand into the chemistry of yttrium and the lanthanides. First, the bimetallic potassium reagent [KCH(PPh2═NSiMe3)(PPh2═S)}]2 was synthesized by deprotonation of [CH2(PPh2═NSiMe3)(PPh2═S)] with KH. [KCH(PPh2═NSiMe3)(PPh2═S)}]2 forms a dimeric structure in the solid state. The potassium atoms are

  （亚氨基磷烷基）（硫代膦烷基）甲烷CH（PPh 2 ＝ NSiMe 3）（PPh 2 ＝ S）} -已作为配体引入到钇和镧系元素的化学反应中。首先，双金属钾试剂[K CH（PPH 2 ═NSiMe 3）（PPH 2 = S）}] 2通过的[CH去质子化合成2（PPH 2 ═NSiMe 3）（PPH 2 = S）]与KH 。[K CH（PPH 2 ═NSiMe 3）（PPH 2 = S）}] 2形成固态的二聚体结构。钾原子被配体的硫原子桥接。此外，η 6一个苯基环的协调是观察。[K CH（PPH的盐复分解2 ═NSiMe 3）（PPH 2 = S）}] 2与LnCl 3导致二氯络合物[CH（PPH 2 ═NSiMe 3）（PPH 2 = S）} LnCl 2（THF）]（Ln ＝ Dy，Er）。双（酰氨基）化合物[CH（PPH 2 ═NSiMe 3）（PPH 2 = S）} LN
• {CH ₂ (PPh ₂ =NSiMe ₃ )(PPh ₂ =S)} and {CH(PPh ₂ =NSiMe ₃ )(Ph ₂ P=S)} ^– as Ligands in Zinc Chemistry: Synthesis and Structures
  作者：Magdalena Kuzdrowska、Balasubramanian Murugesapandian、Larissa Hartenstein、Michael T. Gamer、Nicholas Arleth、Siegfried Blechert、Peter W. Roesky

  DOI：10.1002/ejic.201300501

  日期：2013.9.10

  metallacycle (N–P–C–P–S–Zn). The reaction of CH2(PPh2=NSiMe3)(PPh2=S)} with [ZnN(SiMe3)2}2] and ZnPh2 resulted in the (iminophosphoranyl)(thiophosphoranyl)methanide complexes [(PPh2=NSiMe3)(PPh2=S)CH}ZnN(SiMe3)2}] and [(PPh2=NSiMe3)(PPh2=S)CH}ZnPh], respectively. In addition to the coordination of the phosphinimine nitrogen and sulfur atoms to the zinc atom, a long contact between the methine carbon

  (亚氨基正膦基)(硫代正膦基)甲烷锌配合物[(PPh2=NSiMe3)(PPh2=S)CH2}ZnX2](X=Cl,I)由CH2(PPh2=NSiMe3)(PPh2= S)} 与相应的二卤化锌 ZnCl2 和 ZnI2。（亚氨基正膦基）（硫代正膦基）甲烷配体作为双齿配体通过氮和硫原子与锌原子配位形成六元金属环（N-P-C-P-S-Zn）。CH2(PPh2=NSiMe3)(PPh2=S)} 与 [ZnN(SiMe3)2}2] 和 ZnPh2 的反应产生了（亚氨基正膦基）（硫代正膦基）甲烷化合物 [(PPh2=NSiMe3)(PPh2 =S)CH}ZnN(SiMe3)2}] 和 [(PPh2=NSiMe3)(PPh2=S)CH}ZnPh]。除了膦亚胺氮和硫原子与锌原子的配位，在这些配合物中观察到 P-C-P 桥的次甲基碳原子和锌原子之间的长接触。所有新化合物的固态结构均通过单晶 X
• Synthesis and Characterization of Magnesium and Aluminum Bis(phosphoranyl)methanediide Complexes
  作者：Jiayi Guo、Jia-Shin Lee、Ming-Choo Foo、Kai-Chung Lau、Hong-Wei Xi、Kok Hwa Lim、Cheuk-Wai So

  DOI：10.1021/om900985f

  日期：2010.2.22

  The reaction of [CH2(PPh2=NSiMe3)(PPh2=E)] (E = S (1), NSiMe3 (2)) with Mg(Bu-II)(2) in refluxing toluene afforded the magnesium bis(phosphoranyl)methanediide complexes [(PPh2=NSiMe3)(PPh2=E)}CMg](2) (E = S (3), NSiMe3 (4)), respectively. The X-ray structures and DFT calculations of 3 and 4 show that they are bimetallic methanediide complexes of magnesium containing a strong Mg-C-methanediide electrostatic bonding. Treatment of 4 with water in toluene gave 2 and the magnesium hydroxide complex [HC(PPh2=NSiMe3)(2)Mg(mu-OH)](2) (5), confirmed by X-ray crystallography. The reaction of I with AlMe3 in refluxing toluene afforded the aluminum bis(phosphoranyl)methanediide complex [(PPh2=NSiMe3)(PPh2=S)}CAIMe](2) (6). The X-ray structure of 6 shows that a methanediide carbon is bonded to one aluminum atom. DFT calculations of 6 demonstrate that Al-C-methanediide is highly polar with weak covalent bonding, consistent with the topological analysis of electron densities of 6.