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B–H Functionalization of Hydrogen-Rich [(Cp*V)2(B2H6)2]: Synthesis and Structures of [(Cp*V)2(B2X2)2H8] (X = Cl, SePh; Cp* = η5-C5Me5)
Organometallics ( IF 2.5 ) Pub Date : 2019-12-16 , DOI: 10.1021/acs.organomet.9b00609
Anagha Haridas 1 , Sourav Kar 1 , Beesam Raghavendra 1 , Thierry Roisnel 2 , Vincent Dorcet 2 , Sundargopal Ghosh 1
Affiliation  

We have recently reported the perchlorinated diniobaborane species [(Cp*Nb)2(B2H4Cl2)2] from [(Cp*Nb)2(B2H6)2] using CCl4 as a chlorinating agent. In an attempt to isolate the vanadium analogue, we have isolated [(Cp*V)2(B2H6)2] (1) from the reaction of (Cp*VCl2)3 with [LiBH4·THF] followed by thermolysis with excess [BH3·THF]. Subsequently, the thermolysis of 1 with CCl4 for a prolonged period of time afforded the perchlorinated divanadaborane [(Cp*V)2(B2H4Cl2)2] (2) along with the formation of the bichlorinated divanadaborane [(Cp*V)2(B2H5Cl)2] (3) and trichlorinated divanadaborane [(Cp*V)2(B2H4Cl2)(B2H5Cl)] (4). Similarly, in order to functionalize the terminal B–H by a {SePh} group, thermolysis of 1 was carried out with Ph2Se2, which yielded the persubstituted divanadaborane [(Cp*V)2{B2H4(SePh)2}2] (5) in parallel to the formation of [(Cp*V)2{B4H11(SePh)}] (6). Compound 5 is very fascinating in that all of the terminal B–H hydrogens of 1 have been substituted by {SePh} ligands. All of the compounds have been characterized by 1H, 11B, and 13C NMR spectroscopy, mass spectrometry, IR spectroscopy, and single-crystal X-ray analysis. Density functional theory (DFT) and TD-DFT calculations provided a further understanding regarding the electronic structures, bonding, and electronic transitions of these persubstituted vanadaborane species.

中文翻译:

富氢[(Cp * V)2(B 2 H 62 ]的B–H官能化:[(Cp * V)2(B 2 X 22 H 8 ]的合成和结构(X = Cl, SEPH;的Cp * =η 5 -C 55

最近,我们报道了使用CCl 4作为氯化剂从[(Cp * Nb)2(B 2 H 62 ]中得到的全氯二异丁烷硼烷物质[(Cp * Nb)2(B 2 H 4 Cl 22 ] 。为了分离钒类似物,我们从(Cp * VCl 23与[LiBH 4 ·THF]的反应中分离了[(Cp * V)2(B 2 H 62 ](1),然后过量[BH 3·THF]。随后,将1与CCl 4长时间热解,可得到全氯代二硼硼烷[(Cp * V)2(B 2 H 4 Cl 22 ](2),以及氯代二硼硼烷[(Cp * V)2(B 2 H 5 Cl)2 ](3)和三氯化二钒硼烷[(Cp * V)2(B 2 H 4 Cl 2)(B 2 H 5 Cl)](4)。类似地,为了通过{SePh}基团官能化末端B–H,用Ph 2 Se 2进行1的热解,生成了全取代的二钒硼烷[(Cp * V)2 {B 2 H 4(SePh)2 } 2 ](5)平行于[(Cp * V)2 {B 4 H 11(SePh)}](6)的形成。化合物5是非常引人入胜中,所有的终端B-H的氢的1已经由{SEPH}配位体取代。所有化合物的特征是1 H,11 B和13 C NMR光谱,质谱,IR光谱和单晶X射线分析。密度泛函理论(DFT)和TD-DFT计算提供了有关这些全取代的钒硼烷物种的电子结构,键合和电子跃迁的进一步理解。
更新日期:2019-12-17
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