B-H Bond Activation by an Amidinate-Stabilized Amidosilylene: Non-Innocent Amidinate Ligand

Sabrina Khoo; Yu Liang Shan; Ming Chung Yang; Yongxin Li; Ming Der Su; Cheuk Wai So

doi:10.1021/acs.inorgchem.8b00321

B-H Bond Activation by an Amidinate-Stabilized Amidosilylene: Non-Innocent Amidinate Ligand

Sabrina Khoo, Yu Liang Shan, Ming Chung Yang, Yongxin Li, Ming Der Su^*, Cheuk Wai So

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

31 Citations (Scopus)

Abstract

The activation of B-H and B-Cl bonds in boranes by base-stabilized low-valent silicon compounds is described. The reaction of the amidinato amidosilylene-borane adduct [L{Ar(Me₃Si)N}SiBH₃] [1; L = PhC(NtBu)₂, and Ar = 2,6-iPr₂C₆H₃] with MeOTf in toluene at room temperature formed [L{Ar(Me₃Si)N}SiBH₂OTf] (2). [LSiN(SiMe₃)Ar] in compound 2 then underwent a B-H bond activation with BH₂OTf in refluxing toluene to afford the B-H bond activation product [LB(H)Si(H)(OTf){N(SiMe₃)Ar}] (3). On the other hand, when compound 2 was reacted with 4-dimethylaminopyridine in refluxing toluene, another B-H bond activation product [(μ-κ1: κ1-L)B(H)(DMAP)Si(H){N(Ar)SiMe₃}]OTf (4) was afforded. Mechanistic studies show that "(μ- κ1: κ1-L)B(H)(OTf)Si(H){N(Ar)SiMe₃}" (2A) is the key intermediate in the reactions mentioned above. The formation of 2A is further evidenced by the activation of the B-Cl bond in PhBCl₂ by the amidinato silicon(I) dimer [LSi:]₂ to form the B-Cl bond activation product [(μ- κ1: κ1-L)B(Cl)(Ph)Si(Cl)]₂ (6). Compounds 2-4 and 6 were characterized by nuclear magnetic resonance spectroscopy and X-ray crystallography.

Original language	English
Pages (from-to)	5879-5887
Number of pages	9
Journal	Inorganic Chemistry
Volume	57
Issue number	10
DOIs	https://doi.org/10.1021/acs.inorgchem.8b00321
Publication status	Published - May 21 2018
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2018 American Chemical Society.

ASJC Scopus Subject Areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{cbce9f3b98554cb2b51fe4e75253f565,

title = "B-H Bond Activation by an Amidinate-Stabilized Amidosilylene: Non-Innocent Amidinate Ligand",

abstract = "The activation of B-H and B-Cl bonds in boranes by base-stabilized low-valent silicon compounds is described. The reaction of the amidinato amidosilylene-borane adduct [L{Ar(Me3Si)N}SiBH3] [1; L = PhC(NtBu)2, and Ar = 2,6-iPr2C6H3] with MeOTf in toluene at room temperature formed [L{Ar(Me3Si)N}SiBH2OTf] (2). [LSiN(SiMe3)Ar] in compound 2 then underwent a B-H bond activation with BH2OTf in refluxing toluene to afford the B-H bond activation product [LB(H)Si(H)(OTf){N(SiMe3)Ar}] (3). On the other hand, when compound 2 was reacted with 4-dimethylaminopyridine in refluxing toluene, another B-H bond activation product [(μ-κ1: κ1-L)B(H)(DMAP)Si(H){N(Ar)SiMe3}]OTf (4) was afforded. Mechanistic studies show that {"}(μ- κ1: κ1-L)B(H)(OTf)Si(H){N(Ar)SiMe3}{"} (2A) is the key intermediate in the reactions mentioned above. The formation of 2A is further evidenced by the activation of the B-Cl bond in PhBCl2 by the amidinato silicon(I) dimer [LSi:]2 to form the B-Cl bond activation product [(μ- κ1: κ1-L)B(Cl)(Ph)Si(Cl)]2 (6). Compounds 2-4 and 6 were characterized by nuclear magnetic resonance spectroscopy and X-ray crystallography.",

author = "Sabrina Khoo and Shan, {Yu Liang} and Yang, {Ming Chung} and Yongxin Li and Su, {Ming Der} and So, {Cheuk Wai}",

note = "Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

month = may,

day = "21",

doi = "10.1021/acs.inorgchem.8b00321",

language = "English",

volume = "57",

pages = "5879--5887",

journal = "Inorganic Chemistry",

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TY - JOUR

T1 - B-H Bond Activation by an Amidinate-Stabilized Amidosilylene

T2 - Non-Innocent Amidinate Ligand

AU - Khoo, Sabrina

AU - Shan, Yu Liang

AU - Yang, Ming Chung

AU - Li, Yongxin

AU - Su, Ming Der

AU - So, Cheuk Wai

PY - 2018/5/21

Y1 - 2018/5/21

N2 - The activation of B-H and B-Cl bonds in boranes by base-stabilized low-valent silicon compounds is described. The reaction of the amidinato amidosilylene-borane adduct [L{Ar(Me3Si)N}SiBH3] [1; L = PhC(NtBu)2, and Ar = 2,6-iPr2C6H3] with MeOTf in toluene at room temperature formed [L{Ar(Me3Si)N}SiBH2OTf] (2). [LSiN(SiMe3)Ar] in compound 2 then underwent a B-H bond activation with BH2OTf in refluxing toluene to afford the B-H bond activation product [LB(H)Si(H)(OTf){N(SiMe3)Ar}] (3). On the other hand, when compound 2 was reacted with 4-dimethylaminopyridine in refluxing toluene, another B-H bond activation product [(μ-κ1: κ1-L)B(H)(DMAP)Si(H){N(Ar)SiMe3}]OTf (4) was afforded. Mechanistic studies show that "(μ- κ1: κ1-L)B(H)(OTf)Si(H){N(Ar)SiMe3}" (2A) is the key intermediate in the reactions mentioned above. The formation of 2A is further evidenced by the activation of the B-Cl bond in PhBCl2 by the amidinato silicon(I) dimer [LSi:]2 to form the B-Cl bond activation product [(μ- κ1: κ1-L)B(Cl)(Ph)Si(Cl)]2 (6). Compounds 2-4 and 6 were characterized by nuclear magnetic resonance spectroscopy and X-ray crystallography.

AB - The activation of B-H and B-Cl bonds in boranes by base-stabilized low-valent silicon compounds is described. The reaction of the amidinato amidosilylene-borane adduct [L{Ar(Me3Si)N}SiBH3] [1; L = PhC(NtBu)2, and Ar = 2,6-iPr2C6H3] with MeOTf in toluene at room temperature formed [L{Ar(Me3Si)N}SiBH2OTf] (2). [LSiN(SiMe3)Ar] in compound 2 then underwent a B-H bond activation with BH2OTf in refluxing toluene to afford the B-H bond activation product [LB(H)Si(H)(OTf){N(SiMe3)Ar}] (3). On the other hand, when compound 2 was reacted with 4-dimethylaminopyridine in refluxing toluene, another B-H bond activation product [(μ-κ1: κ1-L)B(H)(DMAP)Si(H){N(Ar)SiMe3}]OTf (4) was afforded. Mechanistic studies show that "(μ- κ1: κ1-L)B(H)(OTf)Si(H){N(Ar)SiMe3}" (2A) is the key intermediate in the reactions mentioned above. The formation of 2A is further evidenced by the activation of the B-Cl bond in PhBCl2 by the amidinato silicon(I) dimer [LSi:]2 to form the B-Cl bond activation product [(μ- κ1: κ1-L)B(Cl)(Ph)Si(Cl)]2 (6). Compounds 2-4 and 6 were characterized by nuclear magnetic resonance spectroscopy and X-ray crystallography.

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U2 - 10.1021/acs.inorgchem.8b00321

DO - 10.1021/acs.inorgchem.8b00321

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VL - 57

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EP - 5887

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 10

ER -

B-H Bond Activation by an Amidinate-Stabilized Amidosilylene: Non-Innocent Amidinate Ligand

Abstract

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