Pearce Kyle G, Simenok Vladimir, Crossley Ian R
Department of Chemistry, University of Sussex, Brighton, UK.
Dalton Trans. 2020 May 7;49(17):5482-5492. doi: 10.1039/d0dt00864h. Epub 2020 Apr 7.
Glutaryl and adipoyl chlorides undergo facile condensation with the bis(silyl)phosphanes RP(SiMe) (R = Me, Bu, Bu, Ph, Mes) to afford exclusively the phosphacycloalkyldiones (CH)(C[double bond, length as m-dash]O)PR (n = 3, 4). Characterised spectroscopically and, for R = Ph, Mes (n = 3) crystallographically, the macrocycles are conformationally fluxional in solution and appreciably moisture sensitive. Though seemingly resistant to chemical oxidation at phosphorus, coordination is readily achieved, as illustrated by isolation of trans-[Pt(PEt){P(Ph)(CO)(CH)}Cl] and a series of tungsten pentacarbonyl complexes, which are characterised crystallographically and by infrared and NMR spectroscopy. Together, these data suggest the macrocycles to be relatively weak σ-donors with no appreciable π-acceptor character.
戊二酰氯和己二酰氯与双（硅基）膦RP(SiMe)（R = 甲基、丁基、叔丁基、苯基、均三甲苯基）容易发生缩合反应，专一性地生成磷杂环烷基二酮(CH)(C[双键，长度如m破折号]O)PR（n = 3, 4）。通过光谱表征，并且对于R = 苯基、均三甲苯基（n = 3）进行了晶体学表征，这些大环在溶液中构象具有流动性，并且对水分相当敏感。尽管在磷原子处似乎对化学氧化有抗性，但很容易实现配位，如分离出反式-[Pt(PEt){P(Ph)(CO)(CH)}Cl]和一系列五羰基钨配合物所示，这些配合物通过晶体学以及红外和核磁共振光谱进行了表征。综合这些数据表明，这些大环是相对较弱的σ供体，没有明显的π受体特性。
