Gomosta Suman, Saha Koushik, Kaur Urminder, Pathak Kriti, Roisnel Thierry, Phukan Ashwini K, Ghosh Sundargopal
Department of Chemistry , Indian Institute of Technology Madras , Chennai 600036 , India.
Université de Rennes , CNRS, ISCR (Institut des Sciences Chimiques de Rennes)-UMR 6226 , F-35000 Rennes , France.
Inorg Chem. 2019 Aug 5;58(15):9992-9997. doi: 10.1021/acs.inorgchem.9b01126. Epub 2019 Jul 19.
A series of hydroborated η-σ,π-alkene-borane complexes have been synthesized from the reaction of ruthenium-bis(σ)borate complex [Cp*Ru(μ-H)BH(S-CH═S)] () and terminal as well as internal alkynes. Likewise, the reactions of manganese-bis(σ)borate complexes [Mn(CO)(μ-H)BHNCSCH(NL)] (L = NCSCH or H) were explored with terminal alkynes that yielded boratabutadiene complexes [Mn(CO){(NCSCH)N}{(RMeC)═B(HC═CHR)}] [R = phenyl () or -tolyl ()] via triple hydroboration of alkynes. These complexes feature a boratabutadiene ligand that is coordinated to a metal through the η-CBCC mode. To the best of our knowledge, these are the first examples of η--boratabutadiene-coordinated manganese complexes generated by the -hydroboration of alkynes. The steric and electronic effects of the borate ligands have been demonstrated using a less sterically hindered manganese-bis(σ)borate complex, [Mn(CO)(μ-H)BH(HNCSCH)], that generated monohydroborated complexes [(CO)Mn(μ-H)(HNCSCH)B(RC═CHR)] (for , R = Ph and R = H; for , R = -Tol and R = H; for , R = R = Ph). Theoretical studies using density functional theory methods and chemical bonding analyses established the bonding and stability of these species.
通过钌双（σ）硼酸酯配合物[Cp*Ru(μ-H)BH(S-CH═S)]（）与端炔和内炔的反应，合成了一系列硼氢化的η-σ,π-烯烃-硼烷配合物。同样，研究了锰双（σ）硼酸酯配合物[Mn(CO)(μ-H)BHNCSCH(NL)]（L = NCSCH或H）与端炔的反应，通过炔烃的三次硼氢化反应生成了硼杂丁二烯配合物[Mn(CO){(NCSCH)N}{(RMeC)═B(HC═CHR)}] [R = 苯基（）或对甲苯基（）]。这些配合物具有一个通过η-CBCC模式与金属配位的硼杂丁二烯配体。据我们所知，这些是通过炔烃的硼氢化反应生成的η-硼杂丁二烯配位锰配合物的首例。使用空间位阻较小的锰双（σ）硼酸酯配合物[Mn(CO)(μ-H)BH(HNCSCH)]证明了硼酸酯配体的空间和电子效应，该配合物生成了单硼氢化配合物[(CO)Mn(μ-H)(HNCSCH)B(RC═CHR)]（对于，R = Ph且R = H；对于，R = 对甲苯基且R = H；对于，R = R = Ph）。使用密度泛函理论方法和化学键分析的理论研究确定了这些物种的键合和稳定性。
