Reactions of HOSiMe2Ar with Pt-PPh3 complexes leading to Si-C bond activation or formation of a siloxoplatinum complex

Neli Mintcheva; Yasushi Nishihara; Atsunori Mori; Kohtaro Osakada

doi:10.1016/S0022-328X(01)00796-3

Reactions of HOSiMe₂Ar with Pt-PPh₃ complexes leading to Si-C bond activation or formation of a siloxoplatinum complex

Neli Mintcheva, Yasushi Nishihara, Atsunori Mori, Kohtaro Osakada

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

19 Citations (Scopus)

Abstract

PtI₂(PPh₃)₂ reacts with HOSiMe₂(C₆H₄CF₃-4) at 60°C in the presence of AgBF₄ to give a mixture of trans-PtI(C₆H₄CF₃-4)(PPh₃) ₂ (1) and [Pt₂(μ-I)₂(PPh₃)₄](BF ₄)₂ (2). Each of the complexes is isolated and characterized by X-ray crystallography and/or NMR spectroscopy. The ³¹P{¹H}-NMR study of the reaction of AgBF₄ with PtI₂(PPh₃)₂ in acetone-d₆ revealed the formation of trans-[PtI(PPh₃)₂(acetone)]BF₄ (3) although isolation of the cationic complex was not feasible due to its facile conversion to 2. Addition of HOSiMe₂(C₆H₄CF₃-4) and Ag₂O to a toluene solution of trans-PtI(Ph)(PPh₃)₂ causes replacement of the iodo ligand with the siloxo group to afford trans-[Pt(Ph){OSiMe₂(C₆H₄CF ₃-4)}(PPh₃)₂] (4). Crystallographic results of 4 show the coordination of the phenyl, siloxo, and PPh₃ ligands to the square-planar Pt center with a large Pt-O-Si angle. Complex 4 does not decompose below 60°C in a toluene solution, but reacts with CH₂Cl₂ and CHCl₃ at room temperature to form trans-PtCl(Ph)(PPh₃)₂ (5).

Original language	English
Pages (from-to)	61-67
Number of pages	7
Journal	Journal of Organometallic Chemistry
Volume	629
Issue number	1-2
DOIs	https://doi.org/10.1016/S0022-328X(01)00796-3
Publication status	Published - Jun 1 2001
Externally published	Yes

Keywords

Cationic complex
Platinum
Silanol
Siloxo complex
Transmetalation

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Materials Chemistry

Access to Document

10.1016/S0022-328X(01)00796-3

Cite this

@article{221fa59190164d78b7ef52748f196d2b,

title = "Reactions of HOSiMe2Ar with Pt-PPh3 complexes leading to Si-C bond activation or formation of a siloxoplatinum complex",

abstract = "PtI2(PPh3)2 reacts with HOSiMe2(C6H4CF3-4) at 60°C in the presence of AgBF4 to give a mixture of trans-PtI(C6H4CF3-4)(PPh3) 2 (1) and [Pt2(μ-I)2(PPh3)4](BF 4)2 (2). Each of the complexes is isolated and characterized by X-ray crystallography and/or NMR spectroscopy. The 31P{1H}-NMR study of the reaction of AgBF4 with PtI2(PPh3)2 in acetone-d6 revealed the formation of trans-[PtI(PPh3)2(acetone)]BF4 (3) although isolation of the cationic complex was not feasible due to its facile conversion to 2. Addition of HOSiMe2(C6H4CF3-4) and Ag2O to a toluene solution of trans-PtI(Ph)(PPh3)2 causes replacement of the iodo ligand with the siloxo group to afford trans-[Pt(Ph){OSiMe2(C6H4CF 3-4)}(PPh3)2] (4). Crystallographic results of 4 show the coordination of the phenyl, siloxo, and PPh3 ligands to the square-planar Pt center with a large Pt-O-Si angle. Complex 4 does not decompose below 60°C in a toluene solution, but reacts with CH2Cl2 and CHCl3 at room temperature to form trans-PtCl(Ph)(PPh3)2 (5).",

keywords = "Cationic complex, Platinum, Silanol, Siloxo complex, Transmetalation",

author = "Neli Mintcheva and Yasushi Nishihara and Atsunori Mori and Kohtaro Osakada",

note = "Funding Information: This work was supported financially by a Grant-in-aid for Scientific Research from the Ministry of Education, Science, Sports and Culture, Japan. N.M. acknowledges the fellowship from UNESCO.",

year = "2001",

month = jun,

day = "1",

doi = "10.1016/S0022-328X(01)00796-3",

language = "English",

volume = "629",

pages = "61--67",

journal = "Journal of Organometallic Chemistry",

issn = "0022-328X",

publisher = "Elsevier",

number = "1-2",

}

TY - JOUR

T1 - Reactions of HOSiMe2Ar with Pt-PPh3 complexes leading to Si-C bond activation or formation of a siloxoplatinum complex

AU - Mintcheva, Neli

AU - Nishihara, Yasushi

AU - Mori, Atsunori

AU - Osakada, Kohtaro

N1 - Funding Information: This work was supported financially by a Grant-in-aid for Scientific Research from the Ministry of Education, Science, Sports and Culture, Japan. N.M. acknowledges the fellowship from UNESCO.

PY - 2001/6/1

Y1 - 2001/6/1

N2 - PtI2(PPh3)2 reacts with HOSiMe2(C6H4CF3-4) at 60°C in the presence of AgBF4 to give a mixture of trans-PtI(C6H4CF3-4)(PPh3) 2 (1) and [Pt2(μ-I)2(PPh3)4](BF 4)2 (2). Each of the complexes is isolated and characterized by X-ray crystallography and/or NMR spectroscopy. The 31P{1H}-NMR study of the reaction of AgBF4 with PtI2(PPh3)2 in acetone-d6 revealed the formation of trans-[PtI(PPh3)2(acetone)]BF4 (3) although isolation of the cationic complex was not feasible due to its facile conversion to 2. Addition of HOSiMe2(C6H4CF3-4) and Ag2O to a toluene solution of trans-PtI(Ph)(PPh3)2 causes replacement of the iodo ligand with the siloxo group to afford trans-[Pt(Ph){OSiMe2(C6H4CF 3-4)}(PPh3)2] (4). Crystallographic results of 4 show the coordination of the phenyl, siloxo, and PPh3 ligands to the square-planar Pt center with a large Pt-O-Si angle. Complex 4 does not decompose below 60°C in a toluene solution, but reacts with CH2Cl2 and CHCl3 at room temperature to form trans-PtCl(Ph)(PPh3)2 (5).

AB - PtI2(PPh3)2 reacts with HOSiMe2(C6H4CF3-4) at 60°C in the presence of AgBF4 to give a mixture of trans-PtI(C6H4CF3-4)(PPh3) 2 (1) and [Pt2(μ-I)2(PPh3)4](BF 4)2 (2). Each of the complexes is isolated and characterized by X-ray crystallography and/or NMR spectroscopy. The 31P{1H}-NMR study of the reaction of AgBF4 with PtI2(PPh3)2 in acetone-d6 revealed the formation of trans-[PtI(PPh3)2(acetone)]BF4 (3) although isolation of the cationic complex was not feasible due to its facile conversion to 2. Addition of HOSiMe2(C6H4CF3-4) and Ag2O to a toluene solution of trans-PtI(Ph)(PPh3)2 causes replacement of the iodo ligand with the siloxo group to afford trans-[Pt(Ph){OSiMe2(C6H4CF 3-4)}(PPh3)2] (4). Crystallographic results of 4 show the coordination of the phenyl, siloxo, and PPh3 ligands to the square-planar Pt center with a large Pt-O-Si angle. Complex 4 does not decompose below 60°C in a toluene solution, but reacts with CH2Cl2 and CHCl3 at room temperature to form trans-PtCl(Ph)(PPh3)2 (5).

KW - Cationic complex

KW - Platinum

KW - Silanol

KW - Siloxo complex

KW - Transmetalation

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U2 - 10.1016/S0022-328X(01)00796-3

DO - 10.1016/S0022-328X(01)00796-3

M3 - Article

AN - SCOPUS:0042370481

SN - 0022-328X

VL - 629

SP - 61

EP - 67

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

IS - 1-2

ER -