Synthesis, NMR characterisation and X-ray structures of mixed chalcogenido PNP ligands containing tellurium: crystal structures of (SePr2PNP)-Pr-i(H)Pr-i(2) and [NaN((EPPr2)-Pr-i)(2)](infinity) (E = Se, Te)

Stuart D. Robertson, Tristram Chivers

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24 Citations (Scopus)

Abstract

Reaction of HN((PPr2)-Pr-i)(2) with one equivalent of selenium in hexane at room temperature yields the monoselenide as the P-H tautomer Se=(PPr2)-Pr-i-N=P(H)Pr-i(2) (2b). Deprotonation of 2b with (n)butyllithium in the presence of TMEDA at -78 degrees C followed by addition of tellurium produces the air-sensitive, mixed chalcogenido complex [(TMEDA)Li((SePPr)-Pr-i,)((TePPr)-Pr-i,)N] (8Li) in > 97% purity after recrystallisation. Similarly, deprotonation of Te=(PPr2)-Pr-i-N=P(H)Pr-i(2), (2c), followed by addition of sulfur, gives the sulfur analogue [(TMEDA)Li((SPPr2)-Pr-i)((TePPr2)-Pr-i)N] (Mi) in > 99% purity. The symmetrical complexes [(TMEDA)Li(SePiPr,),N] (4Li) and [(TMEDA)Li((TePPr2)-Pr-i),N] (Ki) are produced by similar methods. Compounds 2b, 4Li, 5Li, 7Li and 8Li were characterised in solution by multinuclear (H-1, P-31, Se-77 and Te-125) NMR spectroscopy and their solid-state structures were determined by X-ray crystallography. The X-ray crystal structures of the polymeric chains [NaN((EPPr2)-Pr-i,)(2)](infinity) (4Na, E = Se and 5Na, E = Te) are also reported.

LanguageEnglish
Pages1765-1772
Number of pages8
JournalDalton Transactions
Issue number13
Early online date20 Feb 2008
DOIs
Publication statusPublished - 7 Apr 2008

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Tellurium
Deprotonation
Crystal structure
Nuclear magnetic resonance
Ligands
Sulfur
X rays
X ray crystallography
Hexanes
Selenium
Nuclear magnetic resonance spectroscopy
Crystallization
Air
phenyllithium
Temperature
N,N,N',N'-tetramethylethylenediamine

Keywords

  • single source precursors
  • chemical-vapor-deposition
  • thin-films
  • coordination chemistry
  • organophosphorous ligands
  • COMPLEXES
  • CD
  • gallium
  • bond
  • HG

Cite this

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title = "Synthesis, NMR characterisation and X-ray structures of mixed chalcogenido PNP ligands containing tellurium: crystal structures of (SePr2PNP)-Pr-i(H)Pr-i(2) and [NaN((EPPr2)-Pr-i)(2)](infinity) (E = Se, Te)",
abstract = "Reaction of HN((PPr2)-Pr-i)(2) with one equivalent of selenium in hexane at room temperature yields the monoselenide as the P-H tautomer Se=(PPr2)-Pr-i-N=P(H)Pr-i(2) (2b). Deprotonation of 2b with (n)butyllithium in the presence of TMEDA at -78 degrees C followed by addition of tellurium produces the air-sensitive, mixed chalcogenido complex [(TMEDA)Li((SePPr)-Pr-i,)((TePPr)-Pr-i,)N] (8Li) in > 97{\%} purity after recrystallisation. Similarly, deprotonation of Te=(PPr2)-Pr-i-N=P(H)Pr-i(2), (2c), followed by addition of sulfur, gives the sulfur analogue [(TMEDA)Li((SPPr2)-Pr-i)((TePPr2)-Pr-i)N] (Mi) in > 99{\%} purity. The symmetrical complexes [(TMEDA)Li(SePiPr,),N] (4Li) and [(TMEDA)Li((TePPr2)-Pr-i),N] (Ki) are produced by similar methods. Compounds 2b, 4Li, 5Li, 7Li and 8Li were characterised in solution by multinuclear (H-1, P-31, Se-77 and Te-125) NMR spectroscopy and their solid-state structures were determined by X-ray crystallography. The X-ray crystal structures of the polymeric chains [NaN((EPPr2)-Pr-i,)(2)](infinity) (4Na, E = Se and 5Na, E = Te) are also reported.",
keywords = "single source precursors, chemical-vapor-deposition, thin-films, coordination chemistry, organophosphorous ligands, COMPLEXES, CD, gallium, bond, HG",
author = "Robertson, {Stuart D.} and Tristram Chivers",
year = "2008",
month = "4",
day = "7",
doi = "10.1039/b717287g",
language = "English",
pages = "1765--1772",
journal = "Dalton Transactions",
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TY - JOUR

T1 - Synthesis, NMR characterisation and X-ray structures of mixed chalcogenido PNP ligands containing tellurium

T2 - Dalton Transactions

AU - Robertson, Stuart D.

AU - Chivers, Tristram

PY - 2008/4/7

Y1 - 2008/4/7

N2 - Reaction of HN((PPr2)-Pr-i)(2) with one equivalent of selenium in hexane at room temperature yields the monoselenide as the P-H tautomer Se=(PPr2)-Pr-i-N=P(H)Pr-i(2) (2b). Deprotonation of 2b with (n)butyllithium in the presence of TMEDA at -78 degrees C followed by addition of tellurium produces the air-sensitive, mixed chalcogenido complex [(TMEDA)Li((SePPr)-Pr-i,)((TePPr)-Pr-i,)N] (8Li) in > 97% purity after recrystallisation. Similarly, deprotonation of Te=(PPr2)-Pr-i-N=P(H)Pr-i(2), (2c), followed by addition of sulfur, gives the sulfur analogue [(TMEDA)Li((SPPr2)-Pr-i)((TePPr2)-Pr-i)N] (Mi) in > 99% purity. The symmetrical complexes [(TMEDA)Li(SePiPr,),N] (4Li) and [(TMEDA)Li((TePPr2)-Pr-i),N] (Ki) are produced by similar methods. Compounds 2b, 4Li, 5Li, 7Li and 8Li were characterised in solution by multinuclear (H-1, P-31, Se-77 and Te-125) NMR spectroscopy and their solid-state structures were determined by X-ray crystallography. The X-ray crystal structures of the polymeric chains [NaN((EPPr2)-Pr-i,)(2)](infinity) (4Na, E = Se and 5Na, E = Te) are also reported.

AB - Reaction of HN((PPr2)-Pr-i)(2) with one equivalent of selenium in hexane at room temperature yields the monoselenide as the P-H tautomer Se=(PPr2)-Pr-i-N=P(H)Pr-i(2) (2b). Deprotonation of 2b with (n)butyllithium in the presence of TMEDA at -78 degrees C followed by addition of tellurium produces the air-sensitive, mixed chalcogenido complex [(TMEDA)Li((SePPr)-Pr-i,)((TePPr)-Pr-i,)N] (8Li) in > 97% purity after recrystallisation. Similarly, deprotonation of Te=(PPr2)-Pr-i-N=P(H)Pr-i(2), (2c), followed by addition of sulfur, gives the sulfur analogue [(TMEDA)Li((SPPr2)-Pr-i)((TePPr2)-Pr-i)N] (Mi) in > 99% purity. The symmetrical complexes [(TMEDA)Li(SePiPr,),N] (4Li) and [(TMEDA)Li((TePPr2)-Pr-i),N] (Ki) are produced by similar methods. Compounds 2b, 4Li, 5Li, 7Li and 8Li were characterised in solution by multinuclear (H-1, P-31, Se-77 and Te-125) NMR spectroscopy and their solid-state structures were determined by X-ray crystallography. The X-ray crystal structures of the polymeric chains [NaN((EPPr2)-Pr-i,)(2)](infinity) (4Na, E = Se and 5Na, E = Te) are also reported.

KW - single source precursors

KW - chemical-vapor-deposition

KW - thin-films

KW - coordination chemistry

KW - organophosphorous ligands

KW - COMPLEXES

KW - CD

KW - gallium

KW - bond

KW - HG

U2 - 10.1039/b717287g

DO - 10.1039/b717287g

M3 - Article

SP - 1765

EP - 1772

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 13

ER -