TY - JOUR
T1 - Reactivity of Aluminum Complexes of Redox-Active Ligand toward N-Heterocyclic Carbene and Its Thione
AU - Sokolov, Vladimir G.
AU - Koptseva, Tatyana S.
AU - Rumyantcev, Roman V.
AU - Yang, Xiao Juan
AU - Zhao, Yanxia
AU - Fedushkin, Igor L.
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2020/1/13
Y1 - 2020/1/13
N2 - The reaction of dialane (dpp-Bian)Al-Al(dpp-Bian) (1) (dpp-Bian is dianion of 1,2-bis[(2,6-diisopropylphenyl)imino]-acenaphthene) with 1 mol equiv of 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (iPr2ImMe) results in the Al-carbene adduct (dpp-Bian)(iPr2ImMe)Al-Al(dpp-Bian) (3). In the course of the reaction of dialane 1 with 2 mol equiv of 1,3-diisopropyl-4,5-dimethylimidazol-2-thione (iPr2ImtMe) a half of the thione amount undergoes a cleavage of sulfur-carbon double bond. In the product (dpp-Bian)(iPr2ImMe)Al(μ-S)Al(iPr2ImtMe)(dpp-Bian) (4) aluminum atoms coordinate carbene as well as thione ligands. Compound 4 is thermally robust: No reduction of Câ• S bond in thione moiety by the dpp-Bian ligands could be observed in toluene for 24 h at 100 °C. Complex {(dpp-Bian)(iPr2ImMe)Al}2(μ-S) (5) was isolated from the reaction of dialane 1, iPr2ImMe, and iPr2ImtMe (1:1:1). The reaction of mononuclear (dpp-Bian)AlH(THF) (2) (THF = tetrahydrofuran) affords compound (dpp-Bian)AlH(iPr2ImMe) (6). Compounds 3-6 were characterized by 1H NMR and IR spectroscopy; their molecular structures were established by single-crystal X-ray analysis.
AB - The reaction of dialane (dpp-Bian)Al-Al(dpp-Bian) (1) (dpp-Bian is dianion of 1,2-bis[(2,6-diisopropylphenyl)imino]-acenaphthene) with 1 mol equiv of 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene (iPr2ImMe) results in the Al-carbene adduct (dpp-Bian)(iPr2ImMe)Al-Al(dpp-Bian) (3). In the course of the reaction of dialane 1 with 2 mol equiv of 1,3-diisopropyl-4,5-dimethylimidazol-2-thione (iPr2ImtMe) a half of the thione amount undergoes a cleavage of sulfur-carbon double bond. In the product (dpp-Bian)(iPr2ImMe)Al(μ-S)Al(iPr2ImtMe)(dpp-Bian) (4) aluminum atoms coordinate carbene as well as thione ligands. Compound 4 is thermally robust: No reduction of Câ• S bond in thione moiety by the dpp-Bian ligands could be observed in toluene for 24 h at 100 °C. Complex {(dpp-Bian)(iPr2ImMe)Al}2(μ-S) (5) was isolated from the reaction of dialane 1, iPr2ImMe, and iPr2ImtMe (1:1:1). The reaction of mononuclear (dpp-Bian)AlH(THF) (2) (THF = tetrahydrofuran) affords compound (dpp-Bian)AlH(iPr2ImMe) (6). Compounds 3-6 were characterized by 1H NMR and IR spectroscopy; their molecular structures were established by single-crystal X-ray analysis.
UR - http://www.scopus.com/inward/record.url?scp=85077012382&partnerID=8YFLogxK
U2 - 10.1021/acs.organomet.9b00611
DO - 10.1021/acs.organomet.9b00611
M3 - Article
AN - SCOPUS:85077012382
SN - 0276-7333
VL - 39
SP - 66
EP - 73
JO - Organometallics
JF - Organometallics
IS - 1
ER -