Synthesis and Characterization of Tungsten Alkylidene and Alkylidyne Complexes Featuring a New Carbazole-Based Rigid Trianionic ONO 3– Pincer-Type Ligand
Synthesis and Characterization of Tungsten Alkylidene and Alkylidyne Complexes Featuring a New Carbazole-Based Rigid Trianionic ONO 3– Pincer-Type Ligand
复制标题
以新型咔唑基刚性三阴离子ONO 3-钳型配体为特色的亚烷基钨和亚烷基钨配合物的合成和表征
DOI：
10.1021/acs.organomet.0c00150
复制
发表时间：
2020
期刊：
影响因子：
2.8
通讯作者：
Veige, Adam S.
中科院分区：
文献类型：
--
作者：
Mandal, Ushnish;VenkatRamani, Sudarsan;Ghiviriga, Ion;Abboud, Khalil A.;Veige, Adam S.
报道了一种刚性咔唑三阴离子钳形配体及其钨[Cbz-Ono]W═CHtBu(OtBu)(3)和阴离子亚烷基{Ph3PCH3}{[Cbz-Ono]W≡CtBu(OtBu)}(4)的设计和合成。咔唑配体的设计目的是通过限制N原子孤子对来最大化无机烯胺效应，从而实现高平面性。然而，轨道重叠仍然与柔性配体[CF3-ONO]H3(1)相似。中性亚烷基配合物不能合成。用多核核磁共振光谱、燃烧分析、质谱学和单晶X-射线衍射法对其结构进行了表征。密度泛函理论计算表明，在同时含有刚性和柔性配体的亚烷基络合物中存在无机烯胺轨道重叠。
The design and synthesis of a rigid carbazole trianionic pincer ligand and its tungsten alkylidene [CBZ-ONO]W═CHtBu(OtBu) (3) and anionic alkylidyne {Ph3PCH3}{[CBZ-ONO]W≡CtBu(OtBu)} (4) complexes are reported. Designed to maximize the inorganic enamine effect by constraining the N atom lone pair, the carbazole ligand achieves high planarity. However, the orbital overlap remains similar to that of the flexible ligand [CF3–ONO]H3(1). The neutral alkylidyne complex could not be synthesized. The complexes were characterized by multinuclear NMR spectroscopy, combustion analysis, mass spectrometry, and single-crystal X-ray diffraction. DFT calculations reveal an inorganic enamine orbital overlap within the alkylidyne complexes bearing both the rigid and flexible ligands.