Stabilization of R-P(H)A species (A = OH, OR, S, NH2, NHR, NR2, Cl, Br, I) by complexation with chromium and tungsten pentacarbonyls
Stabilization of R-P(H)A species (A = OH, OR, S, NH2, NHR, NR2, Cl, Br, I) by complexation with chromium and tungsten pentacarbonyls
复制标题
通过与铬和五羰基钨络合来稳定 R-P(H)A 物质（A = OH、OR、S、NH2、NHR、NR2、Cl、Br、I）
DOI：
10.1021/om00071a017
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发表时间：
1982
期刊：
影响因子：
2.8
通讯作者：
F. Mathey
中科院分区：
文献类型：
--
作者：
A. Marinetti;F. Mathey
H_2O，MeOH，PhNH_2，Et_2NH）反应，通过切断邻苯二甲醛骨架上的磷桥，得到相应的[RP（H）A] M（CO）_6仲膦配合物（R= Ph，Me）。这些化合物的磷-氢键非常抗氧化。在一种情况下，它已成功地金属化t-BuOK在THE，然后，要么烷基化甲基碘或缩合与二苯甲酮。[PhP（H）-（NHPh）] W（CO）s的磷-氮键在室温下很容易被卤化氢裂解，得到第一个已知的稳定的仲卤代膦配合物[PhP（H）X] W（CO）6（X= Cl，Br，I）。氯代化合物与氨和NaSH在室温下反应，分别得到[PhP（H）NH 2] W（CO）5和S [PhPH-W-（CO）6] 2。在铝试剂存在下，氯代化合物歧化生成等量的[PhPH_2] W（CO）_6和[PhPCl_2] W（CO）_5。这些化合物均为稳定的化合物，其结构经~ 1H NMR、~（31）P NMR、IR、质谱和元素分析确证。
H20, MeOH, PhNH2, Et2NH) to give the corresponding [RP (H) A] M (CO) 6 secondary phosphine complexes (R= Ph, Me) through cleavage of thephosphorus bridge of the phos-phanorbornadiene skeleton. The phosphorus-hydrogen bond of these compounds is veryresistant toward oxidation. In one case, it has been successfully metalated by t-BuOK inTHE and, then, either alkylated by methyl iodide or condensed with benzophenone. The phosphorus-nitrogen bond of [PhP (H)-(NHPh)] W (CO) s is easily cleaved at room temperature by hydrogen halides to give the first known stable secondary halophosphine complexes [PhP (H) X] W (CO) 6 (X= Cl, Br, I). The chloro compound reacts with ammonia and NaSH at room temperature to give, respectively,[PhP (H) NH2] W (CO) 5 and S [PhPH—W-(CO) 6] 2. In the presence of aluminum trichloride, the dismutation of thechloro compound yields equal amounts of [PhPH2] W (CO) 6 and [PhPCl2] W (CO) 5. All these compounds are stable and have been completely characterized by 1H NMR, 31P NMR, IR, and mass spectrometry and elemental analyses.