De'Ath Peter, Elsegood Mark R J, Sanchez-Ballester Noelia M, Smith Martin B
Department of Chemistry, Loughborough University, Loughborough LE11 3TU, UK.
Molecules. 2021 Nov 11;26(22):6809. doi: 10.3390/molecules26226809.
The solid-state behaviour of two series of isomeric, phenol-substituted, aminomethylphosphines, as the free ligands and bound to Pt, have been extensively studied using single crystal X-ray crystallography. In the first library, isomeric diphosphines of the type PhPCHN(Ar)CHPPh [-; Ar = CH(Me)(OH)] and, in the second library, amide-functionalised, isomeric ligands PhPCHN{CHC(O)NH(Ar)}CHPPh [-; Ar = CH(Me)(OH)], were synthesised by reaction of PhPCHOH and the appropriate amine in CHOH, and isolated as colourless solids or oils in good yield. The non-methyl, substituted diphosphines PhPCHN{CHC(O)NH(Ar)}CHPPh [, Ar = 3-CH(OH); , Ar = 4-CH(OH)] and PhPCHN(Ar)CHPPh [, Ar = 3-CH(OH)] were also prepared for comparative purposes. Reactions of -, -, or with PtCl(η-cod) afforded the corresponding square-planar complexes -, -, and in good to high isolated yields. All new compounds were characterised using a range of spectroscopic (H, P{H}, FT-IR) and analytical techniques. Single crystal X-ray structures have been determined for , ∙CHOH, ∙CHOH, , , ∙(CH)SO, ∙CHCl, ∙½EtO, ∙½CHCl∙½CHOH, ∙½EtO, , ∙¼HO, ∙EtO, and ∙(CH)SO. The free phenolic group in ∙CHOH, ∙CHOH, ∙(CH)SO, ∙½EtO, ∙¼HO, and ∙(CH)SO exhibits various intra- or intermolecular O-H∙∙∙X (X = O, N, P, Cl) hydrogen contacts leading to different packing arrangements.
利用单晶X射线晶体学对两个系列的异构、苯酚取代的氨基甲基膦作为游离配体以及与铂结合时的固态行为进行了广泛研究。在第一个文库中，合成了PhPCHN(Ar)CHPPh类型的异构二膦[-；Ar = CH(Me)(OH)]，在第二个文库中，合成了酰胺官能化的异构配体PhPCHN{CHC(O)NH(Ar)}CHPPh [-；Ar = CH(Me)(OH)]，方法是使PhPCHOH与适当的胺在CHOH中反应，并以高收率分离为无色固体或油状物。还制备了非甲基取代的二膦PhPCHN{CHC(O)NH(Ar)}CHPPh [，Ar = 3-CH(OH)；，Ar = 4-CH(OH)]和PhPCHN(Ar)CHPPh [，Ar = 3-CH(OH)]用于比较。-、-或与PtCl(η-cod)反应，以良好至高的分离产率得到相应的平面正方形配合物-、-和。使用一系列光谱（H、P{H}、FT-IR）和分析技术对所有新化合物进行了表征。已确定了、∙CHOH、∙CHOH、、、∙(CH)SO、∙CHCl、∙½EtO、∙½CHCl∙½CHOH、∙½EtO、、∙¼HO、∙EtO和∙(CH)SO的单晶X射线结构。∙CHOH、∙CHOH、∙(CH)SO、∙½EtO、∙¼HO和∙(CH)SO中的游离酚基表现出各种分子内或分子间的O-H∙∙∙X（X = O、N、P、Cl）氢键，导致不同的堆积排列。
