Synthesis, properties, and reactions of monosulfonated triphenylphosphine (PPh2(m-C6H4SO3K) = TPPMS) complexes of iridium(I). Crystal and molecular structure of [N(CH2C6H5)(C2H5) 3+][PPh2(m-C6H4SO 3)-]·H2O

Paul J. Roman; David P. Paterniti; Ronald F. See; Melvyn Rowen Churchill; Jim D. Atwood

doi:10.1021/om960911a

Synthesis, properties, and reactions of monosulfonated triphenylphosphine (PPh₂(m-C₆H₄SO₃K) = TPPMS) complexes of iridium(I). Crystal and molecular structure of [N(CH₂C₆H₅)(C₂H₅) ₃⁺][PPh₂(m-C₆H₄SO ₃)^-]·H₂O

Paul J. Roman
, David P. Paterniti
, Ronald F. See
, Melvyn Rowen Churchill
, Jim D. Atwood

Chemistry

University at Buffalo

SUNY Buffalo

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

26 Scopus citations

Abstract

Iridium complexes containing the TPPMS ligand (TPPMS = PPh₂(m-C₆H₄SO₃K)) have been prepared and studied in DMSO and H₂O as a comparison to the PPh₃ analogues in toluene. Measurements of the pH of the complexes show that most are almost neutral, but Ir(CO)(H)(TPPMS)₃ is basic (pH = 10.7). The basicity of Ir(CO)(H)(TPPMS)₃ is confirmed by its reaction with H₂O to give Ir(CO)(H)₂(TPPMS)₃⁺. In aqueous solution, reaction of trans-Ir(CO)(OH)(TPPMS)₂ with H₂ produces only fac-Ir(CO)(H)₃(TPPMS)₂ not the usual mixture of facial and meridional isomers. This is attributed to a hydrogen-bonding interaction between the two cis-TPPMS ligands in H₂O. Reaction of trans-Ir(CO)(Cl)(TPPMS)₂ with CO in water produces [Ir(CO)₂(TPPMS)₂⁺]Cl^- and [Ir(CO)₃(TPPMS)₂⁺]Cl sequentially in a reaction that is pH dependent. Reaction of trans-Ir(CO)(OH)(TPPMS)₂ with CO results in products based on the water gas shift-reaction. These complexes of TPPMS are spectroscopically very similar to the PPh₃ analogues, but display significantly different reactions in H₂O.

Original language	English
Pages (from-to)	1484-1490
Number of pages	7
Journal	Organometallics
Volume	16
Issue number	7
DOIs	https://doi.org/10.1021/om960911a
State	Published - Apr 1 1997

Access to Document

10.1021/om960911a

Fingerprint

Dive into the research topics of 'Synthesis, properties, and reactions of monosulfonated triphenylphosphine (PPh₂(m-C₆H₄SO₃K) = TPPMS) complexes of iridium(I). Crystal and molecular structure of [N(CH₂C₆H₅)(C₂H₅) ₃⁺][PPh₂(m-C₆H₄SO ₃)^-]·H₂O'. Together they form a unique fingerprint.

Cite this

@article{d73be772d3ed41a9b0593976b15cb71a,

title = "Synthesis, properties, and reactions of monosulfonated triphenylphosphine (PPh2(m-C6H4SO3K) = TPPMS) complexes of iridium(I). Crystal and molecular structure of [N(CH2C6H5)(C2H5) 3+][PPh2(m-C6H4SO 3)-]·H2O",

abstract = "Iridium complexes containing the TPPMS ligand (TPPMS = PPh2(m-C6H4SO3K)) have been prepared and studied in DMSO and H2O as a comparison to the PPh3 analogues in toluene. Measurements of the pH of the complexes show that most are almost neutral, but Ir(CO)(H)(TPPMS)3 is basic (pH = 10.7). The basicity of Ir(CO)(H)(TPPMS)3 is confirmed by its reaction with H2O to give Ir(CO)(H)2(TPPMS)3+. In aqueous solution, reaction of trans-Ir(CO)(OH)(TPPMS)2 with H2 produces only fac-Ir(CO)(H)3(TPPMS)2 not the usual mixture of facial and meridional isomers. This is attributed to a hydrogen-bonding interaction between the two cis-TPPMS ligands in H2O. Reaction of trans-Ir(CO)(Cl)(TPPMS)2 with CO in water produces [Ir(CO)2(TPPMS)2+]Cl- and [Ir(CO)3(TPPMS)2+]Cl sequentially in a reaction that is pH dependent. Reaction of trans-Ir(CO)(OH)(TPPMS)2 with CO results in products based on the water gas shift-reaction. These complexes of TPPMS are spectroscopically very similar to the PPh3 analogues, but display significantly different reactions in H2O.",

author = "Roman, \{Paul J.\} and Paterniti, \{David P.\} and See, \{Ronald F.\} and Churchill, \{Melvyn Rowen\} and Atwood, \{Jim D.\}",

year = "1997",

month = apr,

day = "1",

doi = "10.1021/om960911a",

language = "English",

volume = "16",

pages = "1484--1490",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "7",

}

Synthesis, properties, and reactions of monosulfonated triphenylphosphine (PPh₂(m-C₆H₄SO₃K) = TPPMS) complexes of iridium(I). Crystal and molecular structure of [N(CH₂C₆H₅)(C₂H₅) ₃⁺][PPh₂(m-C₆H₄SO ₃)^-]·H₂O. / Roman, Paul J.; Paterniti, David P.; See, Ronald F. et al.
In: Organometallics, Vol. 16, No. 7, 01.04.1997, p. 1484-1490.

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

TY - JOUR

T1 - Synthesis, properties, and reactions of monosulfonated triphenylphosphine (PPh2(m-C6H4SO3K) = TPPMS) complexes of iridium(I). Crystal and molecular structure of [N(CH2C6H5)(C2H5) 3+][PPh2(m-C6H4SO 3)-]·H2O

AU - Roman, Paul J.

AU - Paterniti, David P.

AU - See, Ronald F.

AU - Churchill, Melvyn Rowen

AU - Atwood, Jim D.

PY - 1997/4/1

Y1 - 1997/4/1

N2 - Iridium complexes containing the TPPMS ligand (TPPMS = PPh2(m-C6H4SO3K)) have been prepared and studied in DMSO and H2O as a comparison to the PPh3 analogues in toluene. Measurements of the pH of the complexes show that most are almost neutral, but Ir(CO)(H)(TPPMS)3 is basic (pH = 10.7). The basicity of Ir(CO)(H)(TPPMS)3 is confirmed by its reaction with H2O to give Ir(CO)(H)2(TPPMS)3+. In aqueous solution, reaction of trans-Ir(CO)(OH)(TPPMS)2 with H2 produces only fac-Ir(CO)(H)3(TPPMS)2 not the usual mixture of facial and meridional isomers. This is attributed to a hydrogen-bonding interaction between the two cis-TPPMS ligands in H2O. Reaction of trans-Ir(CO)(Cl)(TPPMS)2 with CO in water produces [Ir(CO)2(TPPMS)2+]Cl- and [Ir(CO)3(TPPMS)2+]Cl sequentially in a reaction that is pH dependent. Reaction of trans-Ir(CO)(OH)(TPPMS)2 with CO results in products based on the water gas shift-reaction. These complexes of TPPMS are spectroscopically very similar to the PPh3 analogues, but display significantly different reactions in H2O.

AB - Iridium complexes containing the TPPMS ligand (TPPMS = PPh2(m-C6H4SO3K)) have been prepared and studied in DMSO and H2O as a comparison to the PPh3 analogues in toluene. Measurements of the pH of the complexes show that most are almost neutral, but Ir(CO)(H)(TPPMS)3 is basic (pH = 10.7). The basicity of Ir(CO)(H)(TPPMS)3 is confirmed by its reaction with H2O to give Ir(CO)(H)2(TPPMS)3+. In aqueous solution, reaction of trans-Ir(CO)(OH)(TPPMS)2 with H2 produces only fac-Ir(CO)(H)3(TPPMS)2 not the usual mixture of facial and meridional isomers. This is attributed to a hydrogen-bonding interaction between the two cis-TPPMS ligands in H2O. Reaction of trans-Ir(CO)(Cl)(TPPMS)2 with CO in water produces [Ir(CO)2(TPPMS)2+]Cl- and [Ir(CO)3(TPPMS)2+]Cl sequentially in a reaction that is pH dependent. Reaction of trans-Ir(CO)(OH)(TPPMS)2 with CO results in products based on the water gas shift-reaction. These complexes of TPPMS are spectroscopically very similar to the PPh3 analogues, but display significantly different reactions in H2O.

UR - https://www.scopus.com/pages/publications/0001753853

U2 - 10.1021/om960911a

DO - 10.1021/om960911a

M3 - Article

SN - 0276-7333

VL - 16

SP - 1484

EP - 1490

JO - Organometallics

JF - Organometallics

IS - 7