Bifunctional rhodium complex featuring a silyl1,8-naphthyridine si,n-chelate ligand: Cooperation of metal and pendant base for capture and bond-weakening of BH3

Keita Sato; Takashi Komuro; Hisako Hashimoto; Hiromi Tobita

doi:10.1246/CL.200489

Bifunctional rhodium complex featuring a silyl1,8-naphthyridine si,n-chelate ligand: Cooperation of metal and pendant base for capture and bond-weakening of BH₃

Keita Sato, Takashi Komuro, Hisako Hashimoto, Hiromi Tobita

Tohoku University

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

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Abstract

A dirhodium complex bearing a newly-designed silyl1,8-naphthyridine ligand (napySi), [Rh(κ²Si,N-napySi)(H)(μ-Cl)]₂ (1), was synthesized. Reaction of complex 1 with excess BH₃• SMe₂ afforded a mononuclear borane adduct Rh[κ⁴Si,N,H,HnapySi(BH₃)](H)Cl (2), revealing that rhodium and the uncoordinated naphthyridine nitrogen cooperatively captured BH₃ and weakened its two BH bonds. Complex 2 contains a Rh(μ-H)₂B core composed of two RhHB 3-center 2-electron (3c-2e) bonds where one RhH interaction is considerably weakened by strong trans-influence of the silyl ligand moiety.

Original language	English
Pages (from-to)	1431-1434
Number of pages	4
Journal	Chemistry Letters
Volume	49
Issue number	11
DOIs	https://doi.org/10.1246/CL.200489
Publication status	Published - 2020 Nov

Keywords

1,8-Naphthyridine backbone
Bifunctional complex
Silyl ligand

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title = "Bifunctional rhodium complex featuring a silyl1,8-naphthyridine si,n-chelate ligand: Cooperation of metal and pendant base for capture and bond-weakening of BH3",

abstract = "A dirhodium complex bearing a newly-designed silyl1,8-naphthyridine ligand (napySi), [Rh(κ2Si,N-napySi)(H)(μ-Cl)]2 (1), was synthesized. Reaction of complex 1 with excess BH3• SMe2 afforded a mononuclear borane adduct Rh[κ4Si,N,H,HnapySi(BH3)](H)Cl (2), revealing that rhodium and the uncoordinated naphthyridine nitrogen cooperatively captured BH3 and weakened its two BH bonds. Complex 2 contains a Rh(μ-H)2B core composed of two RhHB 3-center 2-electron (3c-2e) bonds where one RhH interaction is considerably weakened by strong trans-influence of the silyl ligand moiety.",

keywords = "1,8-Naphthyridine backbone, Bifunctional complex, Silyl ligand",

author = "Keita Sato and Takashi Komuro and Hisako Hashimoto and Hiromi Tobita",

note = "Funding Information: This work was supported by JSPS KAKENHI Grant Numbers JP15H03782, JP16K05714, and JP19K05490 from the Japan Society for the Promotion of Science (JSPS). We also acknowledge the Research and Analytical Center for Giant Molecules, Tohoku University, for mass spectroscopic measurements and elemental analysis. Publisher Copyright: {\textcopyright} 2020 The Chemical Society of Japan",

year = "2020",

month = nov,

doi = "10.1246/CL.200489",

language = "English",

volume = "49",

pages = "1431--1434",

journal = "Chemistry Letters",

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publisher = "The Chemical Society of Japan",

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T1 - Bifunctional rhodium complex featuring a silyl1,8-naphthyridine si,n-chelate ligand

T2 - Cooperation of metal and pendant base for capture and bond-weakening of BH3

AU - Sato, Keita

AU - Komuro, Takashi

AU - Hashimoto, Hisako

AU - Tobita, Hiromi

N1 - Funding Information: This work was supported by JSPS KAKENHI Grant Numbers JP15H03782, JP16K05714, and JP19K05490 from the Japan Society for the Promotion of Science (JSPS). We also acknowledge the Research and Analytical Center for Giant Molecules, Tohoku University, for mass spectroscopic measurements and elemental analysis. Publisher Copyright: © 2020 The Chemical Society of Japan

PY - 2020/11

Y1 - 2020/11

N2 - A dirhodium complex bearing a newly-designed silyl1,8-naphthyridine ligand (napySi), [Rh(κ2Si,N-napySi)(H)(μ-Cl)]2 (1), was synthesized. Reaction of complex 1 with excess BH3• SMe2 afforded a mononuclear borane adduct Rh[κ4Si,N,H,HnapySi(BH3)](H)Cl (2), revealing that rhodium and the uncoordinated naphthyridine nitrogen cooperatively captured BH3 and weakened its two BH bonds. Complex 2 contains a Rh(μ-H)2B core composed of two RhHB 3-center 2-electron (3c-2e) bonds where one RhH interaction is considerably weakened by strong trans-influence of the silyl ligand moiety.

AB - A dirhodium complex bearing a newly-designed silyl1,8-naphthyridine ligand (napySi), [Rh(κ2Si,N-napySi)(H)(μ-Cl)]2 (1), was synthesized. Reaction of complex 1 with excess BH3• SMe2 afforded a mononuclear borane adduct Rh[κ4Si,N,H,HnapySi(BH3)](H)Cl (2), revealing that rhodium and the uncoordinated naphthyridine nitrogen cooperatively captured BH3 and weakened its two BH bonds. Complex 2 contains a Rh(μ-H)2B core composed of two RhHB 3-center 2-electron (3c-2e) bonds where one RhH interaction is considerably weakened by strong trans-influence of the silyl ligand moiety.

KW - 1,8-Naphthyridine backbone

KW - Bifunctional complex

KW - Silyl ligand

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JO - Chemistry Letters

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Bifunctional rhodium complex featuring a silyl1,8-naphthyridine si,n-chelate ligand: Cooperation of metal and pendant base for capture and bond-weakening of BH₃

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