Syntheses of dinuclear and trinuclear hydridoplatinum complexes with bridging phosphido ligands [Pt(2)H(2)(μ-PR(2))(2) (PEt3)2] (R = tBu, Ph) and [Pt(3)H(2)(μ-PPh(2))(4) (PEt3)2]. Characterization of the triangular intermediate [Pt3H(μ-PPh2)3(PEt3)3] and its chemical properties

Masumi Itazaki, Yasushi Nishihara, Kohtaro Osakada

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Abstract

The reaction of Ph2PH with Pt(PEt3)3 in 2:1 molar ratio produces the linear triplatinum complex [Pt3H2(μ-PPh2)4 (PEt3)2] (1). X-ray crystallography of 1 shows the structure of the complex with two PEt3 ligands at anti positions, while it exists as a mixture of the isomers with PEt3at anti and syn positions. Pt(PEt3)3 reacts with equimolar Ph2PH to afford the dinuclear complex [Pt2H2(μ-PPh2)2 (PEt3)2] (2) and the cyclic trinuclear complex [Pt3H(μ-PPh2)3(PEt3)3] (3) depending on the reaction conditions. A dinuclear platinum(II) complex with a structure similar to 2, [Pt2H2(μ-PtBu2)2 (PEt3)2] (4) , is obtained by the reaction of tBu2PH with Pt(PEt3)3. Isolated complexes 2 and 3 cleanly react with Ph2PH to form 1, indicating that the reaction of Ph2PH with Pt(PEt3)3, giving 1, involves these complexes as the intermediates. Complex 3 contains a triangular Pt3 core with Pt-Pt bonds in the range 2.9784(4) - 2.9983(3) Å, as shown by X-ray crystallography. The 1H NMR spectrum of 3 exhibits the hydrido signal at δ -7.98 accompanied by splitting due to H - P and H - Pt coupling. Complex 3 reacts with Ph3SiH and Ph2SiH2 to give silylplatinum complexes [Pt3(SiHn+1Ph4-n) (μ-PPh2)3(PEt3)2] (5, n = 1; 6, n = 2). Cationic triangular complexes [Pt3 (μ-PPh2)3(PEt3)3]+ I- (7) and [Pt3(μ-PPh2)3 (PEt3)3]+ [B4O4 Ar4(OH)]- (8, Ar = C6H4Me-4; 9, Ar = C6H4F-4; 10, Ar = C6H4 CF3-4) are obtained from the reactions of complex 3 with MeI and with ArB(OH)2, respectively.

Original languageEnglish
Pages (from-to)1610-1621
Number of pages12
JournalOrganometallics
Volume23
Issue number7
DOIs
Publication statusPublished - Mar 29 2004
Externally publishedYes

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X ray crystallography
chemical properties
Chemical properties
Ligands
ligands
synthesis
Platinum
Isomers
Nuclear magnetic resonance
crystallography
platinum
x rays
isomers
nuclear magnetic resonance

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

@article{07dfb68d267942ae84aae578f5d86008,
title = "Syntheses of dinuclear and trinuclear hydridoplatinum complexes with bridging phosphido ligands [Pt(2)H(2)(μ-PR(2))(2) (PEt3)2] (R = tBu, Ph) and [Pt(3)H(2)(μ-PPh(2))(4) (PEt3)2]. Characterization of the triangular intermediate [Pt3H(μ-PPh2)3(PEt3)3] and its chemical properties",
abstract = "The reaction of Ph2PH with Pt(PEt3)3 in 2:1 molar ratio produces the linear triplatinum complex [Pt3H2(μ-PPh2)4 (PEt3)2] (1). X-ray crystallography of 1 shows the structure of the complex with two PEt3 ligands at anti positions, while it exists as a mixture of the isomers with PEt3at anti and syn positions. Pt(PEt3)3 reacts with equimolar Ph2PH to afford the dinuclear complex [Pt2H2(μ-PPh2)2 (PEt3)2] (2) and the cyclic trinuclear complex [Pt3H(μ-PPh2)3(PEt3)3] (3) depending on the reaction conditions. A dinuclear platinum(II) complex with a structure similar to 2, [Pt2H2(μ-PtBu2)2 (PEt3)2] (4) , is obtained by the reaction of tBu2PH with Pt(PEt3)3. Isolated complexes 2 and 3 cleanly react with Ph2PH to form 1, indicating that the reaction of Ph2PH with Pt(PEt3)3, giving 1, involves these complexes as the intermediates. Complex 3 contains a triangular Pt3 core with Pt-Pt bonds in the range 2.9784(4) - 2.9983(3) {\AA}, as shown by X-ray crystallography. The 1H NMR spectrum of 3 exhibits the hydrido signal at δ -7.98 accompanied by splitting due to H - P and H - Pt coupling. Complex 3 reacts with Ph3SiH and Ph2SiH2 to give silylplatinum complexes [Pt3(SiHn+1Ph4-n) (μ-PPh2)3(PEt3)2] (5, n = 1; 6, n = 2). Cationic triangular complexes [Pt3 (μ-PPh2)3(PEt3)3]+ I- (7) and [Pt3(μ-PPh2)3 (PEt3)3]+ [B4O4 Ar4(OH)]- (8, Ar = C6H4Me-4; 9, Ar = C6H4F-4; 10, Ar = C6H4 CF3-4) are obtained from the reactions of complex 3 with MeI and with ArB(OH)2, respectively.",
author = "Masumi Itazaki and Yasushi Nishihara and Kohtaro Osakada",
year = "2004",
month = "3",
day = "29",
doi = "10.1021/om034131v",
language = "English",
volume = "23",
pages = "1610--1621",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
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TY - JOUR

T1 - Syntheses of dinuclear and trinuclear hydridoplatinum complexes with bridging phosphido ligands [Pt(2)H(2)(μ-PR(2))(2) (PEt3)2] (R = tBu, Ph) and [Pt(3)H(2)(μ-PPh(2))(4) (PEt3)2]. Characterization of the triangular intermediate [Pt3H(μ-PPh2)3(PEt3)3] and its chemical properties

AU - Itazaki, Masumi

AU - Nishihara, Yasushi

AU - Osakada, Kohtaro

PY - 2004/3/29

Y1 - 2004/3/29

N2 - The reaction of Ph2PH with Pt(PEt3)3 in 2:1 molar ratio produces the linear triplatinum complex [Pt3H2(μ-PPh2)4 (PEt3)2] (1). X-ray crystallography of 1 shows the structure of the complex with two PEt3 ligands at anti positions, while it exists as a mixture of the isomers with PEt3at anti and syn positions. Pt(PEt3)3 reacts with equimolar Ph2PH to afford the dinuclear complex [Pt2H2(μ-PPh2)2 (PEt3)2] (2) and the cyclic trinuclear complex [Pt3H(μ-PPh2)3(PEt3)3] (3) depending on the reaction conditions. A dinuclear platinum(II) complex with a structure similar to 2, [Pt2H2(μ-PtBu2)2 (PEt3)2] (4) , is obtained by the reaction of tBu2PH with Pt(PEt3)3. Isolated complexes 2 and 3 cleanly react with Ph2PH to form 1, indicating that the reaction of Ph2PH with Pt(PEt3)3, giving 1, involves these complexes as the intermediates. Complex 3 contains a triangular Pt3 core with Pt-Pt bonds in the range 2.9784(4) - 2.9983(3) Å, as shown by X-ray crystallography. The 1H NMR spectrum of 3 exhibits the hydrido signal at δ -7.98 accompanied by splitting due to H - P and H - Pt coupling. Complex 3 reacts with Ph3SiH and Ph2SiH2 to give silylplatinum complexes [Pt3(SiHn+1Ph4-n) (μ-PPh2)3(PEt3)2] (5, n = 1; 6, n = 2). Cationic triangular complexes [Pt3 (μ-PPh2)3(PEt3)3]+ I- (7) and [Pt3(μ-PPh2)3 (PEt3)3]+ [B4O4 Ar4(OH)]- (8, Ar = C6H4Me-4; 9, Ar = C6H4F-4; 10, Ar = C6H4 CF3-4) are obtained from the reactions of complex 3 with MeI and with ArB(OH)2, respectively.

AB - The reaction of Ph2PH with Pt(PEt3)3 in 2:1 molar ratio produces the linear triplatinum complex [Pt3H2(μ-PPh2)4 (PEt3)2] (1). X-ray crystallography of 1 shows the structure of the complex with two PEt3 ligands at anti positions, while it exists as a mixture of the isomers with PEt3at anti and syn positions. Pt(PEt3)3 reacts with equimolar Ph2PH to afford the dinuclear complex [Pt2H2(μ-PPh2)2 (PEt3)2] (2) and the cyclic trinuclear complex [Pt3H(μ-PPh2)3(PEt3)3] (3) depending on the reaction conditions. A dinuclear platinum(II) complex with a structure similar to 2, [Pt2H2(μ-PtBu2)2 (PEt3)2] (4) , is obtained by the reaction of tBu2PH with Pt(PEt3)3. Isolated complexes 2 and 3 cleanly react with Ph2PH to form 1, indicating that the reaction of Ph2PH with Pt(PEt3)3, giving 1, involves these complexes as the intermediates. Complex 3 contains a triangular Pt3 core with Pt-Pt bonds in the range 2.9784(4) - 2.9983(3) Å, as shown by X-ray crystallography. The 1H NMR spectrum of 3 exhibits the hydrido signal at δ -7.98 accompanied by splitting due to H - P and H - Pt coupling. Complex 3 reacts with Ph3SiH and Ph2SiH2 to give silylplatinum complexes [Pt3(SiHn+1Ph4-n) (μ-PPh2)3(PEt3)2] (5, n = 1; 6, n = 2). Cationic triangular complexes [Pt3 (μ-PPh2)3(PEt3)3]+ I- (7) and [Pt3(μ-PPh2)3 (PEt3)3]+ [B4O4 Ar4(OH)]- (8, Ar = C6H4Me-4; 9, Ar = C6H4F-4; 10, Ar = C6H4 CF3-4) are obtained from the reactions of complex 3 with MeI and with ArB(OH)2, respectively.

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U2 - 10.1021/om034131v

DO - 10.1021/om034131v

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VL - 23

SP - 1610

EP - 1621

JO - Organometallics

JF - Organometallics

SN - 0276-7333

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ER -