Synthesis and Characterization of Tungsten Alkylidene and Alkylidyne Complexes Featuring a New Carbazole-Based Rigid Trianionic ONO3– Pincer-Type Ligand,Organometallics

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Synthesis and Characterization of Tungsten Alkylidene and Alkylidyne Complexes Featuring a New Carbazole-Based Rigid Trianionic ONO3– Pincer-Type Ligand
Organometallics ( IF 2.5 ) Pub Date : 2020-05-01 , DOI: 10.1021/acs.organomet.0c00150
Ushnish Mandal ₁ , Sudarsan VenkatRamani ₁ , Ion Ghiviriga ₁ , Khalil A. Abboud ₁ , Adam S. Veige ₁

Affiliation

The design and synthesis of a rigid carbazole trianionic pincer ligand and its tungsten alkylidene [CBZ-ONO]W═CH^tBu(O^tBu) (3) and anionic alkylidyne {Ph₃PCH₃}{[CBZ-ONO]W≡C^tBu(O^tBu)} (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.

中文翻译：

新型基于咔唑的刚性三阴离子ONO ³ –夹型配体的钨亚烷基和亚炔基钨配合物的合成与表征

刚性咔唑三阴离子钳配体的设计和合成及其钨亚烷基[CBZ-ONO]W═CH^吨卜（O^吨卜）（3）和阴离子次烷基{博士₃ PCH ₃ } {[CBZ-ONO]W≡报道了C ^t Bu（O ^t Bu）}（4）络合物。通过限制N原子孤对来最大程度地发挥无机烯胺作用，咔唑配体具有很高的平面度。但是，轨道重叠仍然与柔性配体[CF ₃ –ONO] H ₃（1）。无法合成中性亚烷基复合物。通过多核NMR光谱，燃烧分析，质谱和单晶X射线衍射对复合物进行表征。DFT计算显示出带有刚性和柔性配体的亚烷基配合物中的无机烯胺轨道重叠。

更新日期：2020-06-23

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