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Hydroboration of Alkynes: η4-Alkene-Borane versus η4- E-Boratabutadiene
Suman Gomosta, Koushik Saha, Urminder Kaur, Kriti Pathak,
Published in American Chemical Society
PMID: 31322868
Volume: 58
Issue: 15
Pages: 9992 - 9997
A series of hydroborated η4-σ,π-alkene-borane complexes have been synthesized from the reaction of ruthenium-bis(σ)borate complex [Cp∗Ru(μ-H)2BH(S-CH=S)] (1) and terminal as well as internal alkynes. Likewise, the reactions of manganese-bis(σ)borate complexes [Mn(CO)3(μ-H)2BHNCSC6H4(NL)] (L = NCSC6H4 or H) were explored with terminal alkynes that yielded boratabutadiene complexes [Mn(CO)3{(NCSC6H4)2N}{(R1MeC)=B(HC=CHR1)}] [R1 = phenyl (4a) or p-tolyl (4b)] via triple hydroboration of alkynes. These complexes feature a boratabutadiene ligand that is coordinated to a metal through the η4-CBCC mode. To the best of our knowledge, these are the first examples of η4-E-boratabutadiene-coordinated manganese complexes generated by the trans-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)3(μ-H)2BH(HN2CSC6H4)], that generated monohydroborated complexes [(CO)3Mn(μ-H)2(HN2CSC6H4)B(R1C=CHR2)] (for 6, R1 = Ph and R2 = H; for 7, R1 = p-Tol and R2 = H; for 8, R1 = R2 = Ph). Theoretical studies using density functional theory methods and chemical bonding analyses established the bonding and stability of these species. © 2019 American Chemical Society.
About the journal
JournalData powered by TypesetInorganic Chemistry
PublisherData powered by TypesetAmerican Chemical Society
Open AccessNo