TY - JOUR
T1 - Reactions of Dianionic α-Diimine-Supported Dimagnesium(I) Compound [K(THF)3]2[LMg-MgL] with Nitriles
AU - Wang, Jijiang
AU - Wang, Juju
AU - Shen, Lingyi
AU - Zhao, Yanxia
AU - Wu, Biao
AU - Yang, Xiao Juan
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/7/8
Y1 - 2019/7/8
N2 - The Mg-Mg-bonded compound, [K(THF)3]2[LMg-MgL] (1, L = [(2,6-iPr2C6H3)NC(Me)]2 2-), exhibits good reactivity toward a series of nitriles (RCN). Reaction of 1 with 2.0 equiv of Me3SiCN proceeded through reductive Si-C(CN) bond cleavage to generate the cyanide ions (CN-), which serve as bridges to link the tetrameric complex [L4Mg4(μ-CN)4K4(THF)6] (2). When more (3.0 equiv) of the nitrile substrates Me3SiCN or tBuCN were reacted with 1, both Si-C(CN) [or C-C(CN)] bond cleavage and terminal coordination of the nitriles occurred, leading to the tetramers [L4Mg4(μ-CN)4(RCN)2K4(THF)4] (R = Me3Si, 3 and R = tBu, 4). More interestingly, reaction of precursor 1 with 2.0 equiv of isobutyronitrile (iPrCN) or cyclohexyl nitrile (CyCN) that has α-hydrogen atoms afforded the dinuclear complexes [{K(THF)2LMg(μ-N=C=CMe2)}2] (6) and [{K(Tol)LMg(μ-N=C=CC5H10)}2] (7) with bridging keteniminate ligands, representing a rare reductive deprotonation pathway for nitriles. All products were characterized by X-ray diffraction, NMR, and infrared spectra and density functional theory computations.
AB - The Mg-Mg-bonded compound, [K(THF)3]2[LMg-MgL] (1, L = [(2,6-iPr2C6H3)NC(Me)]2 2-), exhibits good reactivity toward a series of nitriles (RCN). Reaction of 1 with 2.0 equiv of Me3SiCN proceeded through reductive Si-C(CN) bond cleavage to generate the cyanide ions (CN-), which serve as bridges to link the tetrameric complex [L4Mg4(μ-CN)4K4(THF)6] (2). When more (3.0 equiv) of the nitrile substrates Me3SiCN or tBuCN were reacted with 1, both Si-C(CN) [or C-C(CN)] bond cleavage and terminal coordination of the nitriles occurred, leading to the tetramers [L4Mg4(μ-CN)4(RCN)2K4(THF)4] (R = Me3Si, 3 and R = tBu, 4). More interestingly, reaction of precursor 1 with 2.0 equiv of isobutyronitrile (iPrCN) or cyclohexyl nitrile (CyCN) that has α-hydrogen atoms afforded the dinuclear complexes [{K(THF)2LMg(μ-N=C=CMe2)}2] (6) and [{K(Tol)LMg(μ-N=C=CC5H10)}2] (7) with bridging keteniminate ligands, representing a rare reductive deprotonation pathway for nitriles. All products were characterized by X-ray diffraction, NMR, and infrared spectra and density functional theory computations.
UR - http://www.scopus.com/inward/record.url?scp=85068375020&partnerID=8YFLogxK
U2 - 10.1021/acs.organomet.9b00258
DO - 10.1021/acs.organomet.9b00258
M3 - Article
AN - SCOPUS:85068375020
SN - 0276-7333
VL - 38
SP - 2674
EP - 2682
JO - Organometallics
JF - Organometallics
IS - 13
ER -