Gold complexes of ditelluridoimidodiphosphinate ligands - reversible oxidation of Au(I) to Au(III) via insertion of gold into a phosphorus-tellurium bond

Dana J. Eisler, Stuart D. Robertson, Tristram Chivers

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13 Citations (Scopus)

Abstract

The reaction of (THT) AuCl with (TMEDA)Na[N(TePR2)(2)] (R = Ph, i-Pr, t-Bu) produces a series of gold (III) complexes of the type [{R2PNP(Te)R-2}Au(mu-Te)](2) (4a, R = i-Pr; 4b, R = Ph; 4c, R = t-Bu) rather than the expected homoleptic Au(I) complexes of the ditelluridoimidodiphosphinate ligands. A combination of solution- and solid-state NMR studies shows that both cis and trans isomers of 4a-4c are formed in these reactions. X-ray structural determinations of the trans isomers of 4a-4c reveal a centrosymmetric arrangement with a central four-membered Au2Te2 ring formed by the formal insertion of gold into a P-Te bond; this insertion process was shown to be reversible upon addition of PPh3 to 4a to give the monomeric gold(I) complex Ph3PAu[N{TeP(i-Pr)(2)}(2)]. The X-ray structure of cis-4b is also described.

LanguageEnglish
Pages39-46
Number of pages8
JournalCanadian journal of chemistry-Revue canadienne de chimie
Volume87
Issue number1
Early online date11 Jun 2008
DOIs
Publication statusPublished - Jan 2009

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Tellurium
Gold
Phosphorus
Ligands
Isomers
Oxidation
X rays
Nuclear magnetic resonance

Keywords

  • gold
  • tellurium
  • redox
  • X-ray structures
  • imidodiphosphinate
  • single-source-precursors
  • coordination chemistry
  • crystal-structures
  • thin-films
  • deposition
  • HG
  • CD
  • TE
  • ditelluroimidodiphosphinate

Cite this

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title = "Gold complexes of ditelluridoimidodiphosphinate ligands - reversible oxidation of Au(I) to Au(III) via insertion of gold into a phosphorus-tellurium bond",
abstract = "The reaction of (THT) AuCl with (TMEDA)Na[N(TePR2)(2)] (R = Ph, i-Pr, t-Bu) produces a series of gold (III) complexes of the type [{R2PNP(Te)R-2}Au(mu-Te)](2) (4a, R = i-Pr; 4b, R = Ph; 4c, R = t-Bu) rather than the expected homoleptic Au(I) complexes of the ditelluridoimidodiphosphinate ligands. A combination of solution- and solid-state NMR studies shows that both cis and trans isomers of 4a-4c are formed in these reactions. X-ray structural determinations of the trans isomers of 4a-4c reveal a centrosymmetric arrangement with a central four-membered Au2Te2 ring formed by the formal insertion of gold into a P-Te bond; this insertion process was shown to be reversible upon addition of PPh3 to 4a to give the monomeric gold(I) complex Ph3PAu[N{TeP(i-Pr)(2)}(2)]. The X-ray structure of cis-4b is also described.",
keywords = "gold, tellurium, redox, X-ray structures, imidodiphosphinate, single-source-precursors, coordination chemistry, crystal-structures, thin-films, deposition, HG, CD, TE, ditelluroimidodiphosphinate",
author = "Eisler, {Dana J.} and Robertson, {Stuart D.} and Tristram Chivers",
year = "2009",
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T1 - Gold complexes of ditelluridoimidodiphosphinate ligands - reversible oxidation of Au(I) to Au(III) via insertion of gold into a phosphorus-tellurium bond

AU - Eisler, Dana J.

AU - Robertson, Stuart D.

AU - Chivers, Tristram

PY - 2009/1

Y1 - 2009/1

N2 - The reaction of (THT) AuCl with (TMEDA)Na[N(TePR2)(2)] (R = Ph, i-Pr, t-Bu) produces a series of gold (III) complexes of the type [{R2PNP(Te)R-2}Au(mu-Te)](2) (4a, R = i-Pr; 4b, R = Ph; 4c, R = t-Bu) rather than the expected homoleptic Au(I) complexes of the ditelluridoimidodiphosphinate ligands. A combination of solution- and solid-state NMR studies shows that both cis and trans isomers of 4a-4c are formed in these reactions. X-ray structural determinations of the trans isomers of 4a-4c reveal a centrosymmetric arrangement with a central four-membered Au2Te2 ring formed by the formal insertion of gold into a P-Te bond; this insertion process was shown to be reversible upon addition of PPh3 to 4a to give the monomeric gold(I) complex Ph3PAu[N{TeP(i-Pr)(2)}(2)]. The X-ray structure of cis-4b is also described.

AB - The reaction of (THT) AuCl with (TMEDA)Na[N(TePR2)(2)] (R = Ph, i-Pr, t-Bu) produces a series of gold (III) complexes of the type [{R2PNP(Te)R-2}Au(mu-Te)](2) (4a, R = i-Pr; 4b, R = Ph; 4c, R = t-Bu) rather than the expected homoleptic Au(I) complexes of the ditelluridoimidodiphosphinate ligands. A combination of solution- and solid-state NMR studies shows that both cis and trans isomers of 4a-4c are formed in these reactions. X-ray structural determinations of the trans isomers of 4a-4c reveal a centrosymmetric arrangement with a central four-membered Au2Te2 ring formed by the formal insertion of gold into a P-Te bond; this insertion process was shown to be reversible upon addition of PPh3 to 4a to give the monomeric gold(I) complex Ph3PAu[N{TeP(i-Pr)(2)}(2)]. The X-ray structure of cis-4b is also described.

KW - gold

KW - tellurium

KW - redox

KW - X-ray structures

KW - imidodiphosphinate

KW - single-source-precursors

KW - coordination chemistry

KW - crystal-structures

KW - thin-films

KW - deposition

KW - HG

KW - CD

KW - TE

KW - ditelluroimidodiphosphinate

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VL - 87

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