Synthesis, characterization, and reaction chemistry of PtCl2[P(m-C6H4 SO3Na)3]2, an alkyne hydration catalyst

Laura W. Francisco; Debra A. Moreno; Jim D. Atwood

doi:10.1021/om0104870

Synthesis, characterization, and reaction chemistry of PtCl₂[P(m-C₆H₄ SO₃Na)₃]₂, an alkyne hydration catalyst

Laura W. Francisco
, Debra A. Moreno
, Jim D. Atwood

Chemistry

SUNY Buffalo
D'Youville College

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

91 Scopus citations

Abstract

The preparation and reactions of cis-PtCl₂(TPPTS)₂ (TPPTS = P(m-C₆H₄SO₃Na)₃) in aqueous solution are described. In the absence of excess Cl^-, cis-PtCl₂(TPPTS)₂ exists as a mixture with 20% of cis-Pt(Cl)(H₂O)(TPPTS)₂⁺; the aqua complex was prepared independently by reaction with Ag⁺. As a result of the aquation cis-PtCl₂(TPPTS)₂ is slightly acidic. Increasing the pH for a solution of cis-PtCl₂(TPPTS)₂ leads to Pt₂(TPPTS)₄(μ-OH)₂²⁺; a subsequent decrease in pH leads to cis-Pt(OH₂)₂(TPPTS)₂²⁺ and, ultimately, cis-PtCl₂(TPPTS)₂. All of these complexes were characterized by ³¹P and ¹⁹⁵Pt NMR. cis-PtCl₂(TPPTS)₂ functions as an effective hydration catalyst for the water-soluble alkynes 4-pentyn-1-ol and 3-pentyn-1-ol. Both hydrations are stereospecific to 5-hydroxy-2-pentanone. Hydration of 4-pentyn-1-ol occurs by a 5-exo-dig mechanism, while hydration of 3-pentyn-1-ol occurs through a 5-endo-dig mechanism.

Original language	English
Pages (from-to)	4237-4245
Number of pages	9
Journal	Organometallics
Volume	20
Issue number	20
DOIs	https://doi.org/10.1021/om0104870
State	Published - Oct 1 2001

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title = "Synthesis, characterization, and reaction chemistry of PtCl2[P(m-C6H4 SO3Na)3]2, an alkyne hydration catalyst",

abstract = "The preparation and reactions of cis-PtCl2(TPPTS)2 (TPPTS = P(m-C6H4SO3Na)3) in aqueous solution are described. In the absence of excess Cl-, cis-PtCl2(TPPTS)2 exists as a mixture with 20\% of cis-Pt(Cl)(H2O)(TPPTS)2+; the aqua complex was prepared independently by reaction with Ag+. As a result of the aquation cis-PtCl2(TPPTS)2 is slightly acidic. Increasing the pH for a solution of cis-PtCl2(TPPTS)2 leads to Pt2(TPPTS)4(μ-OH)22+; a subsequent decrease in pH leads to cis-Pt(OH2)2(TPPTS)22+ and, ultimately, cis-PtCl2(TPPTS)2. All of these complexes were characterized by 31P and 195Pt NMR. cis-PtCl2(TPPTS)2 functions as an effective hydration catalyst for the water-soluble alkynes 4-pentyn-1-ol and 3-pentyn-1-ol. Both hydrations are stereospecific to 5-hydroxy-2-pentanone. Hydration of 4-pentyn-1-ol occurs by a 5-exo-dig mechanism, while hydration of 3-pentyn-1-ol occurs through a 5-endo-dig mechanism.",

author = "Francisco, \{Laura W.\} and Moreno, \{Debra A.\} and Atwood, \{Jim D.\}",

year = "2001",

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T1 - Synthesis, characterization, and reaction chemistry of PtCl2[P(m-C6H4 SO3Na)3]2, an alkyne hydration catalyst

AU - Francisco, Laura W.

AU - Moreno, Debra A.

AU - Atwood, Jim D.

PY - 2001/10/1

Y1 - 2001/10/1

N2 - The preparation and reactions of cis-PtCl2(TPPTS)2 (TPPTS = P(m-C6H4SO3Na)3) in aqueous solution are described. In the absence of excess Cl-, cis-PtCl2(TPPTS)2 exists as a mixture with 20% of cis-Pt(Cl)(H2O)(TPPTS)2+; the aqua complex was prepared independently by reaction with Ag+. As a result of the aquation cis-PtCl2(TPPTS)2 is slightly acidic. Increasing the pH for a solution of cis-PtCl2(TPPTS)2 leads to Pt2(TPPTS)4(μ-OH)22+; a subsequent decrease in pH leads to cis-Pt(OH2)2(TPPTS)22+ and, ultimately, cis-PtCl2(TPPTS)2. All of these complexes were characterized by 31P and 195Pt NMR. cis-PtCl2(TPPTS)2 functions as an effective hydration catalyst for the water-soluble alkynes 4-pentyn-1-ol and 3-pentyn-1-ol. Both hydrations are stereospecific to 5-hydroxy-2-pentanone. Hydration of 4-pentyn-1-ol occurs by a 5-exo-dig mechanism, while hydration of 3-pentyn-1-ol occurs through a 5-endo-dig mechanism.

AB - The preparation and reactions of cis-PtCl2(TPPTS)2 (TPPTS = P(m-C6H4SO3Na)3) in aqueous solution are described. In the absence of excess Cl-, cis-PtCl2(TPPTS)2 exists as a mixture with 20% of cis-Pt(Cl)(H2O)(TPPTS)2+; the aqua complex was prepared independently by reaction with Ag+. As a result of the aquation cis-PtCl2(TPPTS)2 is slightly acidic. Increasing the pH for a solution of cis-PtCl2(TPPTS)2 leads to Pt2(TPPTS)4(μ-OH)22+; a subsequent decrease in pH leads to cis-Pt(OH2)2(TPPTS)22+ and, ultimately, cis-PtCl2(TPPTS)2. All of these complexes were characterized by 31P and 195Pt NMR. cis-PtCl2(TPPTS)2 functions as an effective hydration catalyst for the water-soluble alkynes 4-pentyn-1-ol and 3-pentyn-1-ol. Both hydrations are stereospecific to 5-hydroxy-2-pentanone. Hydration of 4-pentyn-1-ol occurs by a 5-exo-dig mechanism, while hydration of 3-pentyn-1-ol occurs through a 5-endo-dig mechanism.

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DO - 10.1021/om0104870

M3 - Article

AN - SCOPUS:0035497161

SN - 0276-7333

VL - 20

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JO - Organometallics

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ER -

Synthesis, characterization, and reaction chemistry of PtCl₂[P(m-C₆H₄ SO₃Na)₃]₂, an alkyne hydration catalyst

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