Facile intermolecular phosphine ligand exchange reactions between square planar iridium and platinum centers

Robert L. Rominger; Jeffrey M. McFarland; James R. Jeitler; Jeffrey S. Thompson; Jim D. Atwood

doi:10.1080/00958979408022540

Facile intermolecular phosphine ligand exchange reactions between square planar iridium and platinum centers

Robert L. Rominger
, Jeffrey M. McFarland
, James R. Jeitler
, Jeffrey S. Thompson
, Jim D. Atwood

Chemistry

SUNY Buffalo

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

10 Scopus citations

Abstract

Reactions between square planar complexes, trans-Ir(CO)(R)L₂ (R = Cl, Me; L = PPh₃, P(p-tolyl)₃, PMePh₂), trans-Pt(Cl)(H)L₂ (L' ‘ = PPh₃, P(p-tolyl)₃, PEt₃), cis-Pt(Cl)₂L₂ and trans-Pt(Cl)₂(PEt₃)₂, result in intermolecular exchange of phosphine ligands. Exchange between two iridium complexes is facile; exchanges between iridium and platinum complexes or between two platinum complexes occur with half-lives of hours. The reactions are followed by ³¹P NMR. The reactions are best interpreted as phosphine ligand dissociation with dissociation from iridium occurring more readily than from platinum. The observed phosphine dependence on the rate, L = P(p-tolyl)₃ > PPh₃ > PEt₃ is consistent with a dissociative process. The dissociated phosphine then causes an associative substitution with the other complexes. Associative substitution on square planar iridium(I) complexes are known to occur much more readily than on square planar platinum(II) complexes.

Original language	English
Pages (from-to)	7-18
Number of pages	12
Journal	Journal of Coordination Chemistry
Volume	31
Issue number	1
DOIs	https://doi.org/10.1080/00958979408022540
State	Published - Jan 1 1994

Keywords

iridium
Ligand exchange
platinum
square planar

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10.1080/00958979408022540

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title = "Facile intermolecular phosphine ligand exchange reactions between square planar iridium and platinum centers",

abstract = "Reactions between square planar complexes, trans-Ir(CO)(R)L2 (R = Cl, Me; L = PPh3, P(p-tolyl)3, PMePh2), trans-Pt(Cl)(H)L2 (L' {\textquoteleft} = PPh3, P(p-tolyl)3, PEt3), cis-Pt(Cl)2L2 and trans-Pt(Cl)2(PEt3)2, result in intermolecular exchange of phosphine ligands. Exchange between two iridium complexes is facile; exchanges between iridium and platinum complexes or between two platinum complexes occur with half-lives of hours. The reactions are followed by 31P NMR. The reactions are best interpreted as phosphine ligand dissociation with dissociation from iridium occurring more readily than from platinum. The observed phosphine dependence on the rate, L = P(p-tolyl)3 > PPh3 > PEt3 is consistent with a dissociative process. The dissociated phosphine then causes an associative substitution with the other complexes. Associative substitution on square planar iridium(I) complexes are known to occur much more readily than on square planar platinum(II) complexes.",

keywords = "iridium, Ligand exchange, platinum, square planar",

author = "Rominger, \{Robert L.\} and McFarland, \{Jeffrey M.\} and Jeitler, \{James R.\} and Thompson, \{Jeffrey S.\} and Atwood, \{Jim D.\}",

year = "1994",

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doi = "10.1080/00958979408022540",

language = "English",

volume = "31",

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T1 - Facile intermolecular phosphine ligand exchange reactions between square planar iridium and platinum centers

AU - Rominger, Robert L.

AU - McFarland, Jeffrey M.

AU - Jeitler, James R.

AU - Thompson, Jeffrey S.

AU - Atwood, Jim D.

PY - 1994/1/1

Y1 - 1994/1/1

N2 - Reactions between square planar complexes, trans-Ir(CO)(R)L2 (R = Cl, Me; L = PPh3, P(p-tolyl)3, PMePh2), trans-Pt(Cl)(H)L2 (L' ‘ = PPh3, P(p-tolyl)3, PEt3), cis-Pt(Cl)2L2 and trans-Pt(Cl)2(PEt3)2, result in intermolecular exchange of phosphine ligands. Exchange between two iridium complexes is facile; exchanges between iridium and platinum complexes or between two platinum complexes occur with half-lives of hours. The reactions are followed by 31P NMR. The reactions are best interpreted as phosphine ligand dissociation with dissociation from iridium occurring more readily than from platinum. The observed phosphine dependence on the rate, L = P(p-tolyl)3 > PPh3 > PEt3 is consistent with a dissociative process. The dissociated phosphine then causes an associative substitution with the other complexes. Associative substitution on square planar iridium(I) complexes are known to occur much more readily than on square planar platinum(II) complexes.

AB - Reactions between square planar complexes, trans-Ir(CO)(R)L2 (R = Cl, Me; L = PPh3, P(p-tolyl)3, PMePh2), trans-Pt(Cl)(H)L2 (L' ‘ = PPh3, P(p-tolyl)3, PEt3), cis-Pt(Cl)2L2 and trans-Pt(Cl)2(PEt3)2, result in intermolecular exchange of phosphine ligands. Exchange between two iridium complexes is facile; exchanges between iridium and platinum complexes or between two platinum complexes occur with half-lives of hours. The reactions are followed by 31P NMR. The reactions are best interpreted as phosphine ligand dissociation with dissociation from iridium occurring more readily than from platinum. The observed phosphine dependence on the rate, L = P(p-tolyl)3 > PPh3 > PEt3 is consistent with a dissociative process. The dissociated phosphine then causes an associative substitution with the other complexes. Associative substitution on square planar iridium(I) complexes are known to occur much more readily than on square planar platinum(II) complexes.

KW - iridium

KW - Ligand exchange

KW - platinum

KW - square planar

UR - https://www.scopus.com/pages/publications/84937031145

U2 - 10.1080/00958979408022540

DO - 10.1080/00958979408022540

M3 - Article

AN - SCOPUS:84937031145

SN - 0095-8972

VL - 31

SP - 7

EP - 18

JO - Journal of Coordination Chemistry

JF - Journal of Coordination Chemistry

IS - 1

ER -

Facile intermolecular phosphine ligand exchange reactions between square planar iridium and platinum centers

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