TY - JOUR
T1 - A Nickel Complex Containing a Pyramidalized, Ambiphilic Pincer Germylene Ligand
AU - Watanabe, Takahito
AU - Kasai, Yumi
AU - Tobita, Hiromi
N1 - Funding Information:
This work was supported by Japan Society for the Promotion of Science (JSPS) KAKENHI Grant Numbers 15H03782 and 17K05798. This work was also supported by a Dean's Grant for Exploratory Research (Graduate School of Science, Tohoku University). We are grateful to the Research and Analytical Center for Giant Molecules, Tohoku University, for elemental analysis. Theoretical calculations were performed using the facilities in the Research Center for Computational Science, Okazaki, Japan.
Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2019/10/22
Y1 - 2019/10/22
N2 - Reaction of N-heterocyclic carbene (NHC)-stabilized PGeP-type germylene Ge{o-(PiPr2)C6H4}2⋅MeIiPr (1) (MeIiPr=1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) with Ni(cod)2 gave pincer germylene complex Ni[Ge{o-(PiPr2)C6H4}2](MeIiPr) (2), in which the Ge center of 2 is significantly pyramidalized. Theoretical calculation on 2 predicted the ambiphilicity of the germanium center, which was confirmed by reactivity studies. Thus, complex 2 reacted with both Lewis base MeIMe (MeIMe=1,3,4,5-tetramethylimidazol-2-ylidene) and Lewis acid BH3⋅SMe2 at the germanium center to afford the adducts Ni[Ge{o-(PiPr2)C6H4}2⋅MeIMe](MeIiPr) (3) and Ni[Ge{o-(PiPr2)C6H4}2⋅BH3](MeIiPr) (4), respectively. Furthermore, the former was slowly converted to dinuclear complex Ni2[Ge{o-(PiPr2)C6H4}2]2(MeIMe)2 (5) at room temperature. Complex 5 can be regarded as a dimer of the MeIMe analog of 2 with a Ni-Ge-Ge-Ni linkage.
AB - Reaction of N-heterocyclic carbene (NHC)-stabilized PGeP-type germylene Ge{o-(PiPr2)C6H4}2⋅MeIiPr (1) (MeIiPr=1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) with Ni(cod)2 gave pincer germylene complex Ni[Ge{o-(PiPr2)C6H4}2](MeIiPr) (2), in which the Ge center of 2 is significantly pyramidalized. Theoretical calculation on 2 predicted the ambiphilicity of the germanium center, which was confirmed by reactivity studies. Thus, complex 2 reacted with both Lewis base MeIMe (MeIMe=1,3,4,5-tetramethylimidazol-2-ylidene) and Lewis acid BH3⋅SMe2 at the germanium center to afford the adducts Ni[Ge{o-(PiPr2)C6H4}2⋅MeIMe](MeIiPr) (3) and Ni[Ge{o-(PiPr2)C6H4}2⋅BH3](MeIiPr) (4), respectively. Furthermore, the former was slowly converted to dinuclear complex Ni2[Ge{o-(PiPr2)C6H4}2]2(MeIMe)2 (5) at room temperature. Complex 5 can be regarded as a dimer of the MeIMe analog of 2 with a Ni-Ge-Ge-Ni linkage.
KW - ambiphilic ligands
KW - germanium
KW - germylenes
KW - nickel
KW - pincer ligands
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U2 - 10.1002/chem.201903069
DO - 10.1002/chem.201903069
M3 - Article
C2 - 31437315
AN - SCOPUS:85073666529
SN - 0947-6539
VL - 25
SP - 13491
EP - 13495
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 59
ER -