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 journalArticle

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 languageEnglish
Pages (from-to)61-67
Number of pages7
JournalJournal of Organometallic Chemistry
Volume629
Issue number1-2
DOIs
Publication statusPublished - Jun 1 2001
Externally publishedYes

Fingerprint

Toluene
Acetone
Chemical activation
Ligands
activation
acetone
toluene
X ray crystallography
Nuclear magnetic resonance spectroscopy
nuclear magnetic resonance
ligands
X Ray Crystallography
Nuclear magnetic resonance
crystallography
isolation
Magnetic Resonance Spectroscopy
Temperature
causes
room temperature
spectroscopy

Keywords

  • Cationic complex
  • Platinum
  • Silanol
  • Siloxo complex
  • Transmetalation

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Reactions of HOSiMe2Ar with Pt-PPh3 complexes leading to Si-C bond activation or formation of a siloxoplatinum complex. / Mintcheva, Neli; Nishihara, Yasushi; Mori, Atsunori; Osakada, Kohtaro.

In: Journal of Organometallic Chemistry, Vol. 629, No. 1-2, 01.06.2001, p. 61-67.

Research output: Contribution to journalArticle

@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",
year = "2001",
month = "6",
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

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

UR - http://www.scopus.com/inward/record.url?scp=0042370481&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0042370481&partnerID=8YFLogxK

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

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

M3 - Article

VL - 629

SP - 61

EP - 67

JO - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

IS - 1-2

ER -