(Me2NCS2)Pd(PEt3)[η(1)-C(N(CH3)HC(CH3)3)=CH2] | 164925-28-4

• 分子结构分类: 有机化合物 - 有机硫化合物 - 异硫脲类
• 英文名称: (Me2NCS2)Pd(PEt3)[η(1)-C(N(CH3)HC(CH3)3)=CH2]
• 英文别名: N,N-dimethylcarbamodithioate;N-ethenyl-N,2-dimethylpropan-2-amine;palladium(2+);triethylphosphane
• CAS: 164925-28-4
• 化学式: C₁₆H₃₅N₂PPdS₂
• 分子量: 456.993
• InChiKey: WOZFALBFWODHBD-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  4.57
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  39.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  四氟硼酸-二乙醚络合物 、 (Me2NCS2)Pd(PEt3)[η(1)-C(N(CH3)HC(CH3)3)=CH2] 、 四苯硼钠 以 二氯甲烷 为溶剂， 以73%的产率得到(Me2NCS2)Pd(PEt3)[η(1)-C(N(CH3)C(CH3)3)CH3]BPh4
  参考文献：
  名称：

  Syntheses of carbene and alkenyl derivatives of palladium. Solid-state structures of {(Me2NCS2) Pd(PEt3) [η1−C(N(CH3) C(CH3)3) CH3]}BPh4 and {(Me2NCS2)Pd(PEt3)[η1−C(NHC(CH3)3)CH3]}PF6 · Et2O

  摘要：

  The reaction of (t)BuNC and (Me(2)NCS(2))Pd(PEt(3))CH3 yields (Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(NC(CH3)(3)CH3]. Reaction of this amino acyl complex with [(CH3)(3))]BF4 yields, after anion exchange, {Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(NHC(CH3)(3)CH3]}BPh(4). An analogous reaction with NH4PF6 yields {(Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(NHC(CH3)(3)CH3]}PF6. Both of these carbene complexes have been characterized crystallographically. Crystal data: {(Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(N(CH3)C(CH3)(3))CH3]}BPh(4) triclinic, P (1) over bar, a = 12.253(12) Angstrom, b = 14.422(5) Angstrom, c = 11.564(5) Angstrom, alpha = 97.83(3)degrees, beta = 93.04(6)degrees, gamma = 85.21(5)degrees, V = 2018 Angstrom(3), Z = 2, T = 298 K, R(F) = 7.6%; {(Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(NHC(CH3)(3))CH3]}PF6 . Et(2)O triclinic, P (1) over bar, a = 12.844(2) Angstrom, b = 15.247(2) Angstrom, c = 8.312(2) Angstrom, alpha = 105.60(1)degrees, beta = 101.67(2)degrees, gamma = 90.20(1)degrees, V = 1533 Angstrom(3), Z = 2, T = 298 K, R(F) = 5.4%. In both complexes, the overall coordination geometry is approximately planar about both the palladium atom and carbene carbon atom, and these two planes are perpendicular. Reaction of {(Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(N(CH3)C(CH3)(3))CH3]}BPh(4) with LiCH3 results in deprotonation at the beta-carbon yielding (Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(N(CH3)C(CH3)(3))-CH2], and this reaction is reversed with HBF4 . Et(2)O. The reaction of LiC(OCH2CH3)=CH2 with (Me(2)NCS(2))Pd(PEt(3))Cl yields (Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(OCH2CH3)=CH2]. This alkenyl complex reacts with BH3 in ethanol to yield (Me(2)NCS(2))Pd(PEt(3))[eta(1)-CH(OCH2CH3)CH3]. (Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(OCH2CH3)=CH2] also forms in the reaction of (Me(2)NCS(2))Pd(PEt(3))H and HC=COCH2CH3, along with both geometric isomers of (Me(2)NCS(2))Pd(PEt(3))[eta(1)-CH=CH(OCH2CH3)]. Reaction of phenylacetylene and (Me(2)NCS(2))Pd(PEt(3))H yields mainly (Me(2)NCS(2))Pd(PEt(3)){eta(1)-C(Ph)=CH2) with small amounts of one of the other regioisomers present.

  DOI：

  10.1016/0022-328x(94)05248-a
• 作为产物：
  描述：

  (Me2NCS2)Pd(PEt3)[η(1)-C(N(CH3)C(CH3)3)CH3]BPh4 、 甲基锂 以 四氢呋喃 为溶剂， 以70%的产率得到(Me2NCS2)Pd(PEt3)[η(1)-C(N(CH3)HC(CH3)3)=CH2]
  参考文献：
  名称：

  Syntheses of carbene and alkenyl derivatives of palladium. Solid-state structures of {(Me2NCS2) Pd(PEt3) [η1−C(N(CH3) C(CH3)3) CH3]}BPh4 and {(Me2NCS2)Pd(PEt3)[η1−C(NHC(CH3)3)CH3]}PF6 · Et2O

  摘要：

  The reaction of (t)BuNC and (Me(2)NCS(2))Pd(PEt(3))CH3 yields (Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(NC(CH3)(3)CH3]. Reaction of this amino acyl complex with [(CH3)(3))]BF4 yields, after anion exchange, {Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(NHC(CH3)(3)CH3]}BPh(4). An analogous reaction with NH4PF6 yields {(Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(NHC(CH3)(3)CH3]}PF6. Both of these carbene complexes have been characterized crystallographically. Crystal data: {(Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(N(CH3)C(CH3)(3))CH3]}BPh(4) triclinic, P (1) over bar, a = 12.253(12) Angstrom, b = 14.422(5) Angstrom, c = 11.564(5) Angstrom, alpha = 97.83(3)degrees, beta = 93.04(6)degrees, gamma = 85.21(5)degrees, V = 2018 Angstrom(3), Z = 2, T = 298 K, R(F) = 7.6%; {(Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(NHC(CH3)(3))CH3]}PF6 . Et(2)O triclinic, P (1) over bar, a = 12.844(2) Angstrom, b = 15.247(2) Angstrom, c = 8.312(2) Angstrom, alpha = 105.60(1)degrees, beta = 101.67(2)degrees, gamma = 90.20(1)degrees, V = 1533 Angstrom(3), Z = 2, T = 298 K, R(F) = 5.4%. In both complexes, the overall coordination geometry is approximately planar about both the palladium atom and carbene carbon atom, and these two planes are perpendicular. Reaction of {(Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(N(CH3)C(CH3)(3))CH3]}BPh(4) with LiCH3 results in deprotonation at the beta-carbon yielding (Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(N(CH3)C(CH3)(3))-CH2], and this reaction is reversed with HBF4 . Et(2)O. The reaction of LiC(OCH2CH3)=CH2 with (Me(2)NCS(2))Pd(PEt(3))Cl yields (Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(OCH2CH3)=CH2]. This alkenyl complex reacts with BH3 in ethanol to yield (Me(2)NCS(2))Pd(PEt(3))[eta(1)-CH(OCH2CH3)CH3]. (Me(2)NCS(2))Pd(PEt(3))[eta(1)-C(OCH2CH3)=CH2] also forms in the reaction of (Me(2)NCS(2))Pd(PEt(3))H and HC=COCH2CH3, along with both geometric isomers of (Me(2)NCS(2))Pd(PEt(3))[eta(1)-CH=CH(OCH2CH3)]. Reaction of phenylacetylene and (Me(2)NCS(2))Pd(PEt(3))H yields mainly (Me(2)NCS(2))Pd(PEt(3)){eta(1)-C(Ph)=CH2) with small amounts of one of the other regioisomers present.

  DOI：

  10.1016/0022-328x(94)05248-a