Amidinate-Stabilized Group 9 Metal-Silicon(I) Dimer and -Silylene Complexes

Sabrina Khoo; Hui Xian Yeong; Yongxin Li; Rakesh Ganguly; Cheuk Wai So

doi:10.1021/acs.inorgchem.5b01759

Amidinate-Stabilized Group 9 Metal-Silicon(I) Dimer and -Silylene Complexes

Sabrina Khoo, Hui Xian Yeong, Yongxin Li, Rakesh Ganguly, Cheuk Wai So^*

^*Corresponding author for this work

Nanyang Technological University

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

32 Citations (Scopus)

Abstract

The coordination chemistry of the amidinate-stabilized silicon(I) dimer toward group 9 metal complexes is described. The reaction of [LSi:]₂ (1, L = PhC(NtBu)₂) with [Ir(cod)Cl]₂ (cod = 1,5-cyclooctadiene) in toluene at ambient temperature afforded the base-stabilized silicon(I) dimer-iridium complex [LSi{Ir(cod)-μ-Cl-Ir(cod)}SiL][(cod)IrCl₂] (2). In contrast, the reaction of 1 with [Rh(cod)Cl]₂ in toluene at ambient temperature afforded a mixture of the amidinate-stabilized silicon(I) dimer-rhodium complex [LSi{Rh(cod)-μ-Cl-Rh(cod)}SiL] (3) and the dimeric amidinate-stabilized rhodosilylene [(LSi)μ-{Rh(μ-Cl)₂Rh(cod)}]₂ (4). Moreover, the latter reacted with PPh₃ to afford a mixture of the Wilkinsons catalyst [(PPh₃)₃RhCl] and the dimeric rhodosilylene complex [(LSi)μ-{RhCl(PPh₃)}]₂ (5), which underwent a rearrangement to form the rhodosilylene-phosphidorhodium dimer (LSi)[μ-{RhCl(PPh₃)}μ-{RhCl(LSiPh)}](PPh₂) (6). Compounds 2-6 were characterized by NMR spectroscopy and X-ray crystallography. In addition, DFT calculations of compound 4 were performed to understand its electronic structure.

Original language	English
Pages (from-to)	9968-9975
Number of pages	8
Journal	Inorganic Chemistry
Volume	54
Issue number	20
DOIs	https://doi.org/10.1021/acs.inorgchem.5b01759
Publication status	Published - Oct 19 2015
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2015 American Chemical Society.

ASJC Scopus Subject Areas

Physical and Theoretical Chemistry
Inorganic Chemistry

Access to Document

10.1021/acs.inorgchem.5b01759

Cite this

@article{d8f848b77c464d6faf24571f3284afe1,

title = "Amidinate-Stabilized Group 9 Metal-Silicon(I) Dimer and -Silylene Complexes",

abstract = "The coordination chemistry of the amidinate-stabilized silicon(I) dimer toward group 9 metal complexes is described. The reaction of [LSi:]2 (1, L = PhC(NtBu)2) with [Ir(cod)Cl]2 (cod = 1,5-cyclooctadiene) in toluene at ambient temperature afforded the base-stabilized silicon(I) dimer-iridium complex [LSi{Ir(cod)-μ-Cl-Ir(cod)}SiL][(cod)IrCl2] (2). In contrast, the reaction of 1 with [Rh(cod)Cl]2 in toluene at ambient temperature afforded a mixture of the amidinate-stabilized silicon(I) dimer-rhodium complex [LSi{Rh(cod)-μ-Cl-Rh(cod)}SiL] (3) and the dimeric amidinate-stabilized rhodosilylene [(LSi)μ-{Rh(μ-Cl)2Rh(cod)}]2 (4). Moreover, the latter reacted with PPh3 to afford a mixture of the Wilkinsons catalyst [(PPh3)3RhCl] and the dimeric rhodosilylene complex [(LSi)μ-{RhCl(PPh3)}]2 (5), which underwent a rearrangement to form the rhodosilylene-phosphidorhodium dimer (LSi)[μ-{RhCl(PPh3)}μ-{RhCl(LSiPh)}](PPh2) (6). Compounds 2-6 were characterized by NMR spectroscopy and X-ray crystallography. In addition, DFT calculations of compound 4 were performed to understand its electronic structure.",

author = "Sabrina Khoo and Yeong, {Hui Xian} and Yongxin Li and Rakesh Ganguly and So, {Cheuk Wai}",

note = "Publisher Copyright: {\textcopyright} 2015 American Chemical Society.",

year = "2015",

month = oct,

day = "19",

doi = "10.1021/acs.inorgchem.5b01759",

language = "English",

volume = "54",

pages = "9968--9975",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "20",

}

TY - JOUR

T1 - Amidinate-Stabilized Group 9 Metal-Silicon(I) Dimer and -Silylene Complexes

AU - Khoo, Sabrina

AU - Yeong, Hui Xian

AU - Li, Yongxin

AU - Ganguly, Rakesh

AU - So, Cheuk Wai

PY - 2015/10/19

Y1 - 2015/10/19

N2 - The coordination chemistry of the amidinate-stabilized silicon(I) dimer toward group 9 metal complexes is described. The reaction of [LSi:]2 (1, L = PhC(NtBu)2) with [Ir(cod)Cl]2 (cod = 1,5-cyclooctadiene) in toluene at ambient temperature afforded the base-stabilized silicon(I) dimer-iridium complex [LSi{Ir(cod)-μ-Cl-Ir(cod)}SiL][(cod)IrCl2] (2). In contrast, the reaction of 1 with [Rh(cod)Cl]2 in toluene at ambient temperature afforded a mixture of the amidinate-stabilized silicon(I) dimer-rhodium complex [LSi{Rh(cod)-μ-Cl-Rh(cod)}SiL] (3) and the dimeric amidinate-stabilized rhodosilylene [(LSi)μ-{Rh(μ-Cl)2Rh(cod)}]2 (4). Moreover, the latter reacted with PPh3 to afford a mixture of the Wilkinsons catalyst [(PPh3)3RhCl] and the dimeric rhodosilylene complex [(LSi)μ-{RhCl(PPh3)}]2 (5), which underwent a rearrangement to form the rhodosilylene-phosphidorhodium dimer (LSi)[μ-{RhCl(PPh3)}μ-{RhCl(LSiPh)}](PPh2) (6). Compounds 2-6 were characterized by NMR spectroscopy and X-ray crystallography. In addition, DFT calculations of compound 4 were performed to understand its electronic structure.

AB - The coordination chemistry of the amidinate-stabilized silicon(I) dimer toward group 9 metal complexes is described. The reaction of [LSi:]2 (1, L = PhC(NtBu)2) with [Ir(cod)Cl]2 (cod = 1,5-cyclooctadiene) in toluene at ambient temperature afforded the base-stabilized silicon(I) dimer-iridium complex [LSi{Ir(cod)-μ-Cl-Ir(cod)}SiL][(cod)IrCl2] (2). In contrast, the reaction of 1 with [Rh(cod)Cl]2 in toluene at ambient temperature afforded a mixture of the amidinate-stabilized silicon(I) dimer-rhodium complex [LSi{Rh(cod)-μ-Cl-Rh(cod)}SiL] (3) and the dimeric amidinate-stabilized rhodosilylene [(LSi)μ-{Rh(μ-Cl)2Rh(cod)}]2 (4). Moreover, the latter reacted with PPh3 to afford a mixture of the Wilkinsons catalyst [(PPh3)3RhCl] and the dimeric rhodosilylene complex [(LSi)μ-{RhCl(PPh3)}]2 (5), which underwent a rearrangement to form the rhodosilylene-phosphidorhodium dimer (LSi)[μ-{RhCl(PPh3)}μ-{RhCl(LSiPh)}](PPh2) (6). Compounds 2-6 were characterized by NMR spectroscopy and X-ray crystallography. In addition, DFT calculations of compound 4 were performed to understand its electronic structure.

UR - http://www.scopus.com/inward/record.url?scp=84945261248&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84945261248&partnerID=8YFLogxK

U2 - 10.1021/acs.inorgchem.5b01759

DO - 10.1021/acs.inorgchem.5b01759

M3 - Article

AN - SCOPUS:84945261248

SN - 0020-1669

VL - 54

SP - 9968

EP - 9975

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 20

ER -

Amidinate-Stabilized Group 9 Metal-Silicon(I) Dimer and -Silylene Complexes

Abstract

Bibliographical note

ASJC Scopus Subject Areas

Access to Document

Other files and links

Fingerprint

Cite this