Hydrophosphination of formaldehyde catalysed by tris-(hydroxymethyl)phosphine complexes of platinum, palladium or nickel
Hydrophosphination of formaldehyde catalysed by tris-(hydroxymethyl)phosphine complexes of platinum, palladium or nickel
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铂、钯或镍的三(羟甲基)膦配合物催化甲醛氢膦酸化
DOI：
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发表时间：
1993
期刊：
影响因子：
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通讯作者：
Kerry Worboys
中科院分区：
文献类型：
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作者：
P. Hoye;P. Pringle;Martin B. Smith;Kerry Worboys
PH3 与甲醛加成生成 P(CH2OH)3 是由一系列铂-(IV)、-(II) 和 -(0) 化合物催化的，包括 Na2[PtCl6]、K2[PtCl4]、[PtCl2{P(CH2OH)3}2]2 和 [Pt{P(CH2OH)3}4]·H2O 3。 P(CH2OH)3 到 Pt 存在于催化操作的条件下，并且已经测试了在这些条件下存在常见铂-P(CH2OH)3 络合物的假设。结果表明，Na2[PtCl6] 被 3 当量的 P(CH2OH)3 还原，得到 [PtCl2{P(CH2OH)3}2]2，与将 2 当量的 P(CH2OH)3 添加到 K2[PtCl4] 时形成的物质相同。将 1 当量的 P(CH2OH)3 添加到 2 中，得到 [PtCl{P(CH2OH)3}]3Cl 4a，而将 2 当量的 P(CH2OH)3 添加到 2 中，得到不稳定的物质，暂时指定为五配位结构 [PtCl{P(CH2OH)3}4]Cl 5a。在进一步存在 P(CH2OH)3 的情况下，5a 顺利分解，得到 [PtH{P(CH2OH)3}4]Cl 3b、[P(CH2OH)4]Cl 和不常见的双(螯合物)盐反式和顺式-[Pt{(HOCH2)2PCH2OP(CH2OH)2}2]Cl26a 和 6b 的混合物。提出了合理化该反应的机制。催化过程中反应介质的pH值约为。 9-10，因此得出结论，[Pt{P(CH2OH)3}4]3a 是所有铂催化反应中存在的主要含铂物质。结果表明，[Ni{P(CH2OH)3}4]18 和 [Pd{P(CH2OH)3}4]19 也是甲醛氢膦化的催化剂，并提出了一般机制。
The addition of PH3 to formaldehyde to give P(CH2OH)3 is catalysed by a range of platinum-(IV), -(II) and -(0) compounds including Na2[PtCl6], K2[PtCl4], [PtCl2{P(CH2OH)3}2]2 and [Pt{P(CH2OH)3}4]·H2O 3. A large ratio of P(CH2OH)3 to Pt is present under the conditions in which the catalysis is operated and the hypothesis that a common platinum–P(CH2OH)3 complex is present under these conditions has been tested. It is shown that Na2[PtCl6] is reduced by 3 equivalents of P(CH2OH)3 to give [PtCl2{P(CH2OH)3}2]2, the same species that is formed upon addition of 2 equivalents of P(CH2OH)3 to K2[PtCl4]. Addition of 1 equivalent of P(CH2OH)3 to 2 gives [PtCl{P(CH2OH)3}]3Cl 4a while addition of 2 equivalents of P(CH2OH)3 to 2 gives an unstable species, tentatively assigned the five-co-ordinate structure [PtCl{P(CH2OH)3}4]Cl 5a. In the presence of further P(CH2OH)3, 5a decomposes smoothly to give a mixture of [PtH{P(CH2OH)3}4]Cl 3b, [P(CH2OH)4]Cl and the unusual bis(chelate) salts trans- and cis-[Pt{(HOCH2)2PCH2OP(CH2OH)2}2]Cl26a and 6b. A mechanism rationalising this reaction is presented. The pH of the reaction medium during the catalysis is ca. 9–10 and it is therefore concluded that [Pt{P(CH2OH)3}4]3a is the main platinum-containing species present during all the platinum catalysed reactions. It is shown that [Ni{P(CH2OH)3}4]18 and [Pd{P(CH2OH)3}4]19 are also catalysts for the hydrophosphination of formaldehyde and a general mechanism is suggested.