Synthesis and characterization of rhodium, iridium, and palladium complexes of a diarylamido-based PNSb pincer ligand†,Dalton Transactions

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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 (^iPrPN^HSb^Ph) with one –PPrⁱ₂ and one –SbPh₂ side donor has been synthesized. Three complexes of its amido form were prepared using standard metalation techniques: (^iPrPNSb^Ph)PdCl, (^iPrPNSb^Ph)RhCO, and (^iPrPNSb^Ph)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. (^iPrPNSb^Ph)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 ⁱ₂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 ^Ph）PdCl，（^iPr PNSb ^Ph）RhCO和（^iPr PNSb ^Ph）Ir（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，–SbPh₂供体对金属的贡献较少，且反式影响较小。从–PPh₂到–SbPh₂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–PPh₂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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