trans-[Rh(Cl(CO)(1,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane)2] | 850796-54-2

• 英文名称: trans-[Rh(Cl(CO)(1,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane)2]
• 英文别名: trans-[RhCl(CO)(6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamantyl(Ph))2]
• CAS: 850796-54-2
• 化学式: C₃₃H₄₂ClO₇P₂Rh
• 分子量: 750.998
• InChiKey: XJBHLQPCFXASFE-WXTBPCFTSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
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• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为产物：
  描述：

  1,3,5,7-四甲基-6-苯基-2,4,8-三氧杂-6-磷酰金刚烷 、 di(rhodium)tetracarbonyl dichloride 以 二氯甲烷 为溶剂， 以69%的产率得到trans-[Rh(Cl(CO)(1,3,5,7-tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane)2]
  参考文献：
  名称：

  苯基三氧杂草金刚烷：庞大，坚固，电子贫乏的配体，可提供非常有效的铑（I）加氢甲酰化催化剂。

  摘要：

  笼型膦1,3,5,7-四甲基-6-苯基-2,4,8-三氧杂-6-磷金刚烷（1a）和1,3,5,7-四乙基-6-苯基-2,4，通过酸催化将PhPH（2）添加到适当的β-二酮中来制备8，trioxa-6-phosphaaaadamantane（1b）; 使用的酸（HCl，H（3）PO（4）或H（2）SO（4））及其浓度会影响这些缩合反应的速率和选择性。膦1a和1b与[PdCl（2）（NCPh）（2）]反应形成复合物trans- [PdCl（2）（1a）（2）]（2a）和trans- [PdCl（2）（1b）（ 2）]（2b）为rac和内消旋非对映异构体的混合物。铂（II）的化学反应更为复杂，当将1a或1b添加到[PtCl（2）（cod）]中时，反式[PtCl（2）L（2）]和[Pt（2）Cl（在CH（2）Cl（2）溶液中形成4）L（2）]（L =或）。反式-[MCl（CO）（1a）（2）] M

  DOI：

  10.1039/b418259f

文献信息

• General Routes to Alkyl Phosphatrioxaadamantane Ligands
  作者：Joanne H. Downing、Joëlle Floure、Katie Heslop、Mairi F. Haddow、Jonathan Hopewell、Matteo Lusi、Hirahataya Phetmung、A. Guy Orpen、Paul G. Pringle、Robert I. Pugh、Damaris Zambrano-Williams

  DOI：10.1021/om800141y

  日期：2008.7.1

  The secondary phosphine CgPH (CgP = 6-phospha-2,4,8-trioxa-1,3,5,7-tetramethyladamantyl group) is made in 50% yield by a modification of the literature method (avoiding high pressures of PH3) by bubbling PH3 through an acidified solution of 2,4-pentanedione at 0 degrees C. Under similar conditions the ethyl analogue (Et)CgPH is formed from 3,5-heptanedione in 75% yield. The halophosphines CgPCl and CgPBr are made by treatment of CgPH with N-halosuccinimide. CgPBr is also made by treatment of CgPH with Br-2. Three methods are described for the synthesis of CgPR, where R = alkyl: (a) the previously reported acid-catalyzed condensation reaction of RPH2 with 2,4-pentanedione, which has been extended to R = Pr-i; (b) treatment of CgP(BH3)Li with RX followed by borane deprotection with Et2NH, which has been used for R = Pr-i, benzyl, n-C20H41; (c) treatment of CgPBr with RMgX, which has been used for R = Pr-i, Me. The complexes [PtC12(CgPH)(2)] (1), [PdCl2(CgPH)(2)] (2), [PdCl2(CgPR)(2)] (where R = Pr-i (3a), Cy (3b)), and [PtCl2(CgPR)(2)] (where R = Pr-i (4a), Cy (4b), n-C20H41 (4c)) are described. The crystal structures of CgPH, CgPCl, [CgP(CH2Ph)(2)]Br, CgP(n-C20H41), and complexes 1, 3b, and 4c are reported. From the v(CO) values for trans-[RhCl(CO)(CgPX)(2)], the sigma-donor/pi-acceptor properties of CgPX are in the order X = Pr-i > Me > Ph > H > Cl.