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Synthesis and characterization of rhodium, iridium, and palladium complexes of a diarylamido-based PNSb pincer ligand†
Dalton Transactions ( IF 3.5 ) Pub Date : 2018-07-26 00:00:00 , DOI: 10.1039/c8dt02207k
Alex J. Kosanovich 1, 2, 3, 4 , Aldo M. Jordan 1, 2, 3, 4 , Nattamai Bhuvanesh 1, 2, 3, 4 , Oleg. V. Ozerov 1, 2, 3, 4
Affiliation  

A new diarylmido-based pincer proto ligand (iPrPNHSbPh) with one –PPri2 and one –SbPh2 side donor has been synthesized. Three complexes of its amido form were prepared using standard metalation techniques: (iPrPNSbPh)PdCl, (iPrPNSbPh)RhCO, and (iPrPNSbPh)Ir(COE), where COE = cis-cyclooctene. These complexes were compared with their previously reported analogs incorporating a –PPh2 side donor in place of –SbPh2. The –SbPh2 donor arm is less donating towards the metal and is less strongly trans-influencing, based on the structural and IR spectroscopic analysis of the Rh complexes. The redox potential of the Pd complexes is only marginally affected by the change from –PPh2 to –SbPh2. (iPrPNSbPh)Ir(COE) proved to be a slower and less selective catalyst in the dehydrogenative borylation of terminal alkynes (DHBTA) than its –PPh2 analog.

中文翻译:

基于二芳基酰胺的PNSb钳形配体的铑,铱和钯配合物的合成与表征

合成了一种新的基于二芳基亚胺的钳型原配体(iPr PN H Sb Ph),该配体具有一个–PPr i 2和一个–SbPh 2侧供体。使用标准金属化技术制备了其酰胺形式的三种配合物:(iPr PNSb PhPdCl,(iPr PNSb PhRhCO和(iPr PNSb PhIr(COE),其中COE =顺式环辛烯。将这些复合物与先前报道的掺入–PPh 2侧供体代替–SbPh的类似物进行了比较。2。根据Rh配合物的结构和IR光谱分析,–SbPh 2供体对金属的贡献较少,且反式影响较小。从–PPh 2到–SbPh 2的变化仅略微影响Pd配合物的氧化还原电势。iPr PNSb Ph)Ir(COE)在末端炔烃(DHBTA)的脱氢硼化反应中比–PPh 2类似物被证明是一种速度更慢,选择性更低的催化剂。
更新日期:2018-07-26
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