(trimethylsilyl)phosphine | 83716-84-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (trimethylsilyl)phosphine
• 英文别名: P-trimethylsilyl-C,C-bis(dimethylamino)methylenephosphine；bis(dimethylamino)methylene(trimethylsilyl)phosphane；(Me2N)2C=PSiMe3；N,N,N',N'-tetramethyl-1-trimethylsilylphosphanylidenemethanediamine
• CAS: 83716-84-1
• 化学式: C₈H₂₁N₂PSi
• 分子量: 204.327
• InChiKey: ITCNWCGJWRWITI-UHFFFAOYSA-N

物化性质

• 沸点：
  66-67 °C(Press: 7.5e-3 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  1.98
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (trimethylsilyl)phosphine 在 三乙基硅烷醇 作用下， 以 乙醚 为溶剂， 以75%的产率得到C,C-bis(dimethylamino)methylenephosphine
  参考文献：
  名称：

  Romanenko, V. D.; Sarina, T. V.; Kolotilo, N. V., Journal of general chemistry of the USSR, 1985, vol. 55, # 5, p. 1060 - 1061

  摘要：

  DOI：
• 作为产物：
  描述：

  N,N,N',N',S-pentamethylthiuronium iodide 、 Lithium-bis(trimethylsilyl)phosphid-Monoglyme 以 乙二醇二甲醚 为溶剂， 反应 2.0h， 以73%的产率得到(trimethylsilyl)phosphine
  参考文献：
  名称：

  Simple Alternative Method for the Preparation of Bis(dimethylamino)methylene(trimethylsilyl)phosphane

  摘要：

  通过硫脲盐[(Me2N)2CSMe]I与LiP(SiMe3)2在1,2-二甲氧基乙烷中反应，以良好的产率制备双(二甲基氨基)亚甲基(三甲基甲硅烷基)膦。

  DOI：

  10.1055/s-1995-3867

文献信息

• Reactivity of Carbonyl-Functionalized Phosphaalkenes RC(O)P=C(NMe2)2 (R =tBu, Ph) towards Electrophiles
  作者：Lothar Weber、Stefan Uthmann、Hans-Georg Stammler、Beate Neumann、Wolfgang W. Schoeller、Roland Boese、Dieter Bläser

  DOI：10.1002/(sici)1099-0682(199912)1999:12<2369::aid-ejic2369>3.0.co;2-s

  日期：1999.12

  [RC(OGaMe3)=P(GaMe3)C(NMe2)(2)] (10a,b). In contrast, one molecule of InMe3 was bound to the phosphorus center of the phosphorus compound. Reaction of the phosphaalkenes with [Ni(CO)(4)], [Fe-2(CO)(9)] or [(Z)-cyclooctene}Cr(CO)(5)] also took place at the pnictogen atom, resulting in complexes of the type [RC(O)PM(CO)(n)}C(NMe2)(2)] (R = tBu, Ph; M = Ni, n = 3; Fe, n = 4; Cr, n = 5). The chemical

  羰基官能化磷烯烃 RC(O)P=C(NMe2)(2) [R = tBu (2a), Ph (2b)] 与质子酸和烷基化试剂在二配位磷原子上发生反应，得到膦酰基取代的碳正离子 3a,b 和 4a,b。相反，用 Me3SiOSO2CF3 处理导致甲硅烷基对氧原子的攻击，并形成 [RC(OSiMe3)=PC(NMe2)(2)]SO3CF3 (5a,b)。类似地，路易斯酸 B(C6F5)(3)、Al(tBu)(2)Cl 和 AlMe3 与羰基的氧原子相连。将两当量的 GaMe3 添加到磷烯烃的氧和磷原子中以产生不耐热复合物 [RC(OGaMe3)=P(GaMe3)C(NMe2)(2)] (10a,b)。相比之下，一分子 InMe3 与磷化合物的磷中心结合。磷烯烃与 [Ni(CO)(4)] 的反应，[Fe-2(CO)(9)] 或 [(Z)-环辛烯}Cr(CO)(5)] 也发生在 pnictogen
• Synthesis, Structure, and Coordination Chemistry of P-Acyl-, P-Thiocarbamoyl-, and P-Dithiocarboxyl-Substituted Phosphaalkenes R(X)C−PC(NMe₂)₂ (R = Ph, <i>t</i>Bu, SSiMe₃, N(Ph)SiMe₃; X = O, S)
  作者：Lothar Weber、Stefan Uthmann、Hartmut Bögge、Achim Müller、Hans-Georg Stammler、Beate Neumann

  DOI：10.1021/om980264i

  日期：1998.8.1

  phosphaalkenes R(X)C−PC(NMe2)2 2c [R(X)C = Me3Si−S(S)C] and 2d [R(X)C = Ph(Me3Si)N(S)C]. Heating 2c and 2d with (CO)5MBr (M = Mn, Re) in toluene at 50−80 °C led to complexes [X = 3c (M = Mn, X = S), 3d (M = Mn, X = NPh), 4c (M = Re, X = S), and 4d (M = Re, X = NPh). The X-ray structure analysis of 2c showed extensive π-delocalization of electron density from phosphorus into the CS group. The structure determination

  Me 3 SiP C（NMe 2）2（1）与新戊酰氯和苯甲酰氯反应，得到酰化的磷烯烃RC（O）P C（NMe 2）2 2a（R = t Bu）和2b（R = Ph）。将二硫化碳和异硫氰酸苯酯插入1的P-Si键中，得到官能化的磷烯烃R（X）C-P C（NMe 2）2 2c [R（X）C = Me 3 Si-S（S）C ]和2d [R（X）C = Ph（Me 3 Si）N（S）C]。加热2c和2d在50-80°C的甲苯中使用（CO）5 MBr（M = Mn，Re）生成络合物[X = 3c（M = Mn，X = S），3d（M = Mn，X = NPh），4c（M = Re，X = S）和4d（M = Re，X = NPh）。2c的X射线结构分析表明，电子密度从磷到CS组广泛地π-离域。4d的结构确定表明该分子为三环系统，其外围四元环具有反方向。该有机磷片段用作η 2（P，S）-μ（P）桥联配体，没有在化学磷杂烯优先的配位模式。
• Phosphaalkenes R ¹ C(O)–P=C(NMe ₂ ) ₂ (R ¹ =Ph, 4‐EtC ₆ H ₄ ): Versatile Reagents for 1,3‐Dipolar Cycloadditions to Phosphenium Complexes [Cp(CO) ₂ M = PPh ₂ ] (M = Mo, W)
  作者：Lothar Weber、Gabriel Noveski、Stefan Uthmann、Hans‐Georg Stammler、Beate Neumann

  DOI：10.1002/ejic.200700440

  日期：2007.9

  Reaction Of [CP(CO)(2)M = PPh2] [where M = Mo (2a), W (2b)] with an excess of the phosphaalkenes arylC(O)P=C(NMe2)(2) [where aryl = Ph (3), 4-EtC6H4 (5)] afforded the metallophosphaalkenes [CP(CO)(2)M-a-P=C(aryl)-O-(PPh2)-Ph-b (M-a-P-b)] [where M = Mo, aryl = Ph (4a); M = W, aryl = Ph (4b); M = MO, aryl = 4-EtC6H4 (6a); M = W, aryl = 4-EtC6H4 (6b)] as orange crystals. Compounds 4a,b and 6a,b were characterized

  [CP(CO)(2)M = PPh2] [其中 M = Mo (2a), W (2b)] 与过量的磷烯烃芳基 C(O)P=C(NMe2)(2) [其中芳基= Ph (3), 4-EtC6H4 (5)] 得到金属磷烯烃 [CP(CO)(2)MaP=C(芳基)-O-(PPh2)-Ph-b (MaPb)] [其中 M = Mo，芳基=Ph(4a)；M = W，芳基 = Ph (4b)；M = MO，芳基 = 4-EtC6H4 (6a)；M = W，芳基 = 4-EtC6H4 (6b)]，橙色晶体。化合物4a、b和6a、b通过光谱法(IR、H-1、C-13和P-31 NMR光谱和MS)表征。此外，通过X射线衍射分析确定了3、4a和6b的分子结构。
• Reactivity of the Inversely Polarized Phosphaalkenes RP=C(NMe2)2 (R=tBu, Me3Si, H) towards Arylcarbene Complexes [(CO)5M=C(OEt)Ar] (Ar=Ph, M=Cr, W; Ar=2-MeC6H4, 2-MeOC6H4, M=W)
  作者：Lothar Weber、Marco Meyer、Hans-Georg Stammler、Beate Neumann

  DOI：10.1002/1521-3765(20011217)7:24<5401::aid-chem5401>3.0.co;2-d

  日期：2001.12.17

  phosphaalkene precursor was incorporated in olefins of the type (Me2N)2C=C(OEt)(Ar). Treatment of [(CO)5W=C(OEt)(2-MeOC6H4)] with HP=C(NMe2)2 gave rise to the formation of an E/Z mixture of [[(Me2N)2CH-P=C(OEt)(2-MeOC6H4)]W(CO)5] the organophosphorus ligand of which formally results from a combination of the carbene ligand and the phosphanediyl [P-CH(NMe2)2]. The reactions reported here strongly depend on an

  芳基化的菲舍尔卡宾配合物[（CO）5M = C（OEt）Ar]（Ar = Ph; M = Cr，W; 2-MeC6H4; 2-MeOC6H; M = W）与磷烯烃RP = C（ NMe2）（R = tBu，SiMe3）除了化合物[（RP = C（NMe2）2] M（CO）之外，还提供了新型的磷烯烃络合物[[RP = C（OEt）Ar] M（CO）5]。 5]。仅在R ＝ SiMe 3（E / Z）的情况下，得到复分解产物的混合物，将磷烯烃前体的双（二甲基氨基）亚甲基单元引入（Me 2 N）2 C ＝ C（ OEt）（Ar）。用HP = C（NMe2）2处理[（CO）5W = C（OEt）（2-MeOC6H4）]会形成[[（Me2N）2CH] E / Z混合物-P = C（OEt）（2-MeOC6H4）] W（CO）5]，其有机磷配体正式由卡宾配体和膦二基[P-CH（NMe2）2]组合而成。
• Inversely Polarized Phosphaalkenes as Phosphinidene‐ and Carbene‐Transfer Reagents
  作者：Lothar Weber、Ulrich Lassahn、Hans‐Georg Stammler、Beate Neumann

  DOI：10.1002/ejic.200500454

  日期：2005.11

  (1i) with the ketene leads to the formation of 2-phospha-1,3-butadiene (5). The thermolabile phosphaalkene 8 decomposes into an imid-azolylidene and (tBuP), the latter species spontaneously oligomerizes to (tBuP), (n = 3, 4). Obviously, compounds 1a-e serve as a convenient source of phosphinidenes and the carbene C(NMe2)(2). A Wanzlick-type equilibrium between these species, however, must be excluded according

  反极化磷烯烃 RP=C(NMe2)2 [R = tBu (1a), Cy (1b), 1-Ad (1c), Ph (1d), Mes (1e)] 与过量的二苯基乙烯酮的反应在正戊烷中得到两性离子加合物 (Me2N)(2)CC(O)=CPh2 (2) 和 3,5-dibenzhydrylidene-1,4,2-dioxaphospholanes 4a-e。Ia 与 Ph2C=C=O 在浓乙腈溶液中的反应得到 4a 和 5-benzhydrylidene-2-tert-butyl-4,4-diphenyl-1,2-oxaphospholan-3-one (6a) 作为副产物. 相反，用乙烯酮处理 Me3SiP=C(NMe2)(2) (1i) 导致形成 2-phospha-1,3-butadiene (5)。不耐热的磷烯烃 8 分解为咪唑亚基和 (tBuP)，后者自发地低聚为 (tBuP), (n