A ruthenium-phosphine complex is represented by the formula:
[RuH₁(R-BINAP) m]X n, (I)
wherein R-BINAP is a tertiary phosphine represented by formula (II):
R is hydrogen or metal; X is ClO₄, BF₄ or PF₆; and when l is 0, then m is 1 and nʹ is 2, and when l is 1, then m is 2 and nʹ is 1.
Synthesis methods are (a) Ru₂ Cl₄(R-BINAP)₂(N(C₂H₅)₂) reacted with a salt MX where M is Na, K, Li, Mg or Ag in mixed water and methylene chloride in presence of a quaternary ammonium or phosphonium salt as transfer agent, (b) Ru(R-BINAP) (OAc)₂ reacted with an acid HX with stirring in mixed methylene chloride and methanol; and (c) RuHCl(R-BINAP)₂ reacted with MX in mixed water and methylene chloride in presence of a quaternary ammonium or phosphonium salt, to give complex where l=1, m=2 and nʹ=1.
The complex is used as catalyst in synthesis, especially asymmetric hydrogenation of allyl alcohols, and is effective at pressure even at room temperature, e.g. for making citronellol from geraniol, in high selectivity.
钌膦络合物用以下公式表示
[RuH₁(R-BINAP) m]X n,(I)
其中 R-BINAP 是由式(II)表示的叔膦:
R 为氢或
金属;X 为 ClO₄、BF₄ 或 PF₆;当 l 为 0 时,则 m 为 1,nʹ 为 2,当 l 为 1 时,则 m 为 2,nʹ 为 1。
合成方法为:(a) Ru₂ Cl₄(R-BINAP)₂(N(C₂H₅)₂)与盐 MX 反应,其中 M 为 Na、K、Li、(b) Ru(R-BINAP)(OAc)₂与酸 HX 在
二氯甲烷和
甲醇混合溶液中搅拌反应;(c) RuHCl(R-BINAP)₂ 与 MX 在季
铵盐或
鏻盐存在下在
水和
二氯甲烷混合液中反应,得到 l=1、m=2 和 nʹ=1 的络合物。
该络合物可用作合成催化剂,特别是烯丙基醇的不对称氢化反应,即使在室温下,在压力作用下也有效,例如从
香叶醇制取
香茅醇,选择性很高。