3,4,8,9-Tetramethyl-1lambda5,6-diphosphabicyclo[4.4.0]deca-3,8-diene 1-oxide | 1447045-25-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 磷环化合物
• 英文名称: 3,4,8,9-Tetramethyl-1lambda5,6-diphosphabicyclo[4.4.0]deca-3,8-diene 1-oxide
• 英文别名: 3,4,8,9-tetramethyl-1λ5,6-diphosphabicyclo[4.4.0]deca-3,8-diene 1-oxide
• CAS: 1447045-25-1
• 化学式: C₁₂H₂₀OP₂
• 分子量: 242.238
• InChiKey: GAIKQAVYTRIHAT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.6
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3,4,8,9-Tetramethyl-1lambda5,6-diphosphabicyclo[4.4.0]deca-3,8-diene 1-oxide 以 氘代二甲亚砜 为溶剂， 反应 0.08h， 生成
  参考文献：
  名称：

  Functionalization Reactions Characteristic of a Robust Bicyclic Diphosphane Framework

  摘要：

  The 3,4,8,9-tetramethy1-1,6-diphospha-bicyclo-[4.4.0]deca-3,8-diene (P-2(C6H10)(2)) framework containing a P-P bond has allowed for an unprecedented selectivity toward functionalization of a single phosphorus lone pair with reference to acyclic diphosphane molecules. Functionalization at the second phosphorus atom was found to proceed at a significantly slower rate, thus opening the pathway for obtaining mixed functional groups for a pair of P P bonded lambda(5)-phosphorus atoms. Reactivity with the chalcogen-atom donors MesCNO (Mes = 2,4,6-C6H2Me3) and SSIiPh(3) has allowed for the selective synthesis of the diphosphane chalcogenides OP2(C6H10)(2) (87%), O2P2(C6H10)(2) (94%), SP2(C6H10)(2) (56%), and S2P2(C6H10)(2) (87%). Computational studies indicate that the oxygen atom transfer reactions involve penta-coordinated phosphorus intermediates that have four membered {PONC} cycles. The P E bond dissociation enthalpies in EP2(C6H10)(2) were measured via calorimetric studies to be 134.7 +/- 2.1 kcal/mol for P-O, and 93 +/- 3 kcal/mol for P-S, respectively, in good agreement with the computed values. Additional reactivity with breaking of the P P bond and formation of diphosphinate O3P2(C6H10)(2) was only observed to occur upon heating of dimethylsulfoxide solutions of the precursor. Reactivity of diphosphane P2(C6H10)2 with azides allowed the isolation of monoiminophosphoranes (RN)P-2(C6H10)(2)(R = Mes, CPh3, SiMe3), and treatment with additional MesN3 yielded symmetric and unsymmetric diiminodiphosphoranes (RN)(MesN)P-2(C6H10)(2) (91% for R = Mes). Metalation reactions with the bulky dihninodiphosphorane ligand (MesN)(2)P-2(C6H10)(2) (nppn) allowed for the isolation and characterization of (rippn)Mo(n(3)-C3H5)Cl(CO)(2) (91%), (nppn)NiCl2 (76%), and [(nppn)Ni(eta(3)-2-C3H4Me)][OTf] showing that these ligands provide an attractive preorganized binding pocket for both late and early transition metals.

  DOI：

  10.1021/ic401052a
• 作为产物：
  描述：

  3,4,8,9-tetramethyl-1,6-diphosphabicyclo(4.4.0)deca-3,8-diene 在 2,4,6-三甲基苯甲腈N-氧化物 作用下， 以 乙醚 为溶剂， 反应 0.17h， 以87%的产率得到3,4,8,9-Tetramethyl-1lambda5,6-diphosphabicyclo[4.4.0]deca-3,8-diene 1-oxide
  参考文献：
  名称：

  Functionalization Reactions Characteristic of a Robust Bicyclic Diphosphane Framework

  摘要：

  The 3,4,8,9-tetramethy1-1,6-diphospha-bicyclo-[4.4.0]deca-3,8-diene (P-2(C6H10)(2)) framework containing a P-P bond has allowed for an unprecedented selectivity toward functionalization of a single phosphorus lone pair with reference to acyclic diphosphane molecules. Functionalization at the second phosphorus atom was found to proceed at a significantly slower rate, thus opening the pathway for obtaining mixed functional groups for a pair of P P bonded lambda(5)-phosphorus atoms. Reactivity with the chalcogen-atom donors MesCNO (Mes = 2,4,6-C6H2Me3) and SSIiPh(3) has allowed for the selective synthesis of the diphosphane chalcogenides OP2(C6H10)(2) (87%), O2P2(C6H10)(2) (94%), SP2(C6H10)(2) (56%), and S2P2(C6H10)(2) (87%). Computational studies indicate that the oxygen atom transfer reactions involve penta-coordinated phosphorus intermediates that have four membered {PONC} cycles. The P E bond dissociation enthalpies in EP2(C6H10)(2) were measured via calorimetric studies to be 134.7 +/- 2.1 kcal/mol for P-O, and 93 +/- 3 kcal/mol for P-S, respectively, in good agreement with the computed values. Additional reactivity with breaking of the P P bond and formation of diphosphinate O3P2(C6H10)(2) was only observed to occur upon heating of dimethylsulfoxide solutions of the precursor. Reactivity of diphosphane P2(C6H10)2 with azides allowed the isolation of monoiminophosphoranes (RN)P-2(C6H10)(2)(R = Mes, CPh3, SiMe3), and treatment with additional MesN3 yielded symmetric and unsymmetric diiminodiphosphoranes (RN)(MesN)P-2(C6H10)(2) (91% for R = Mes). Metalation reactions with the bulky dihninodiphosphorane ligand (MesN)(2)P-2(C6H10)(2) (nppn) allowed for the isolation and characterization of (rippn)Mo(n(3)-C3H5)Cl(CO)(2) (91%), (nppn)NiCl2 (76%), and [(nppn)Ni(eta(3)-2-C3H4Me)][OTf] showing that these ligands provide an attractive preorganized binding pocket for both late and early transition metals.

  DOI：

  10.1021/ic401052a

文献信息

• Functionalization Reactions Characteristic of a Robust Bicyclic Diphosphane Framework
  作者：Daniel Tofan、Manuel Temprado、Subhojit Majumdar、Carl D. Hoff、Christopher C. Cummins

  DOI：10.1021/ic401052a

  日期：2013.8.5

  The 3,4,8,9-tetramethy1-1,6-diphospha-bicyclo-[4.4.0]deca-3,8-diene (P-2(C6H10)(2)) framework containing a P-P bond has allowed for an unprecedented selectivity toward functionalization of a single phosphorus lone pair with reference to acyclic diphosphane molecules. Functionalization at the second phosphorus atom was found to proceed at a significantly slower rate, thus opening the pathway for obtaining mixed functional groups for a pair of P P bonded lambda(5)-phosphorus atoms. Reactivity with the chalcogen-atom donors MesCNO (Mes = 2,4,6-C6H2Me3) and SSIiPh(3) has allowed for the selective synthesis of the diphosphane chalcogenides OP2(C6H10)(2) (87%), O2P2(C6H10)(2) (94%), SP2(C6H10)(2) (56%), and S2P2(C6H10)(2) (87%). Computational studies indicate that the oxygen atom transfer reactions involve penta-coordinated phosphorus intermediates that have four membered PONC} cycles. The P E bond dissociation enthalpies in EP2(C6H10)(2) were measured via calorimetric studies to be 134.7 +/- 2.1 kcal/mol for P-O, and 93 +/- 3 kcal/mol for P-S, respectively, in good agreement with the computed values. Additional reactivity with breaking of the P P bond and formation of diphosphinate O3P2(C6H10)(2) was only observed to occur upon heating of dimethylsulfoxide solutions of the precursor. Reactivity of diphosphane P2(C6H10)2 with azides allowed the isolation of monoiminophosphoranes (RN)P-2(C6H10)(2)(R = Mes, CPh3, SiMe3), and treatment with additional MesN3 yielded symmetric and unsymmetric diiminodiphosphoranes (RN)(MesN)P-2(C6H10)(2) (91% for R = Mes). Metalation reactions with the bulky dihninodiphosphorane ligand (MesN)(2)P-2(C6H10)(2) (nppn) allowed for the isolation and characterization of (rippn)Mo(n(3)-C3H5)Cl(CO)(2) (91%), (nppn)NiCl2 (76%), and [(nppn)Ni(eta(3)-2-C3H4Me)][OTf] showing that these ligands provide an attractive preorganized binding pocket for both late and early transition metals.