X-ray crystallographic and solution studies of the pentamethyldiethylenetriamine and tetramethylethylenediamine adducts of lithium diphenylphosphide

Robert Mulvey, K WADE, D R ARMSTRONG, G T WALKER, R SNAITH, W CLEGG, D REED

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Abstract

X-ray crystallographic studies on the lithium diphenylphosphide adducts (Me2NCH2CH2)2NMe2 · LiPPh2 ( 1) and Me2NCH2CH2NMe2 · LiPPh2 (2) are reported. 1 is monomeric, with a terminal PPh2 unit containing a pyramidally coordinated phosphorus atom attached to the four-coordinate metal atom by a Li-P bond of length 2.567(6) Å. 2 crystallizes as dimers, (Me2NCH2CH2NMe2 · LiPPh2)2, with bridging PPh2 units containing (distorted) tetrahedrally coordinated phosphorus atoms: their planar (LiP)2 rings are roughly square-shaped (mean PLiP angle 91°, mean LiP distance 2.61 Å). Discussion of features of these structures is facilitated by ab initio MO calculations on the model systems LiPH2 and (LiPH2)2. Cryoscopic molecular mass measurements and high-field 7Li/31P NMR spectroscopic studies on solutions of 1 and 2 indicate that both solid-state structures are retained in arene solution, though some dissociation of2 into monomers is apparent.
LanguageEnglish
Pages987-993
Number of pages7
JournalPolyhedron
Volume6
Issue number5
DOIs
Publication statusPublished - 1987

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adducts
Lithium
lithium
X rays
Atoms
Phosphorus
phosphorus
atoms
x rays
Molecular mass
Dimers
monomers
Monomers
Metals
dimers
Nuclear magnetic resonance
dissociation
solid state
nuclear magnetic resonance
rings

Keywords

  • lithium diphenylphosphide
  • X-ray crystallography
  • pentamethyldiethylenetriamine

Cite this

Mulvey, Robert ; WADE, K ; ARMSTRONG, D R ; WALKER, G T ; SNAITH, R ; CLEGG, W ; REED, D . / X-ray crystallographic and solution studies of the pentamethyldiethylenetriamine and tetramethylethylenediamine adducts of lithium diphenylphosphide. In: Polyhedron. 1987 ; Vol. 6, No. 5. pp. 987-993.
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abstract = "X-ray crystallographic studies on the lithium diphenylphosphide adducts (Me2NCH2CH2)2NMe2 · LiPPh2 ( 1) and Me2NCH2CH2NMe2 · LiPPh2 (2) are reported. 1 is monomeric, with a terminal PPh2 unit containing a pyramidally coordinated phosphorus atom attached to the four-coordinate metal atom by a Li-P bond of length 2.567(6) {\AA}. 2 crystallizes as dimers, (Me2NCH2CH2NMe2 · LiPPh2)2, with bridging PPh2 units containing (distorted) tetrahedrally coordinated phosphorus atoms: their planar (LiP)2 rings are roughly square-shaped (mean PLiP angle 91°, mean LiP distance 2.61 {\AA}). Discussion of features of these structures is facilitated by ab initio MO calculations on the model systems LiPH2 and (LiPH2)2. Cryoscopic molecular mass measurements and high-field 7Li/31P NMR spectroscopic studies on solutions of 1 and 2 indicate that both solid-state structures are retained in arene solution, though some dissociation of2 into monomers is apparent.",
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X-ray crystallographic and solution studies of the pentamethyldiethylenetriamine and tetramethylethylenediamine adducts of lithium diphenylphosphide. / Mulvey, Robert; WADE, K ; ARMSTRONG, D R ; WALKER, G T ; SNAITH, R ; CLEGG, W ; REED, D .

In: Polyhedron, Vol. 6, No. 5, 1987, p. 987-993.

Research output: Contribution to journalArticle

TY - JOUR

T1 - X-ray crystallographic and solution studies of the pentamethyldiethylenetriamine and tetramethylethylenediamine adducts of lithium diphenylphosphide

AU - Mulvey, Robert

AU - WADE, K

AU - ARMSTRONG, D R

AU - WALKER, G T

AU - SNAITH, R

AU - CLEGG, W

AU - REED, D

PY - 1987

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N2 - X-ray crystallographic studies on the lithium diphenylphosphide adducts (Me2NCH2CH2)2NMe2 · LiPPh2 ( 1) and Me2NCH2CH2NMe2 · LiPPh2 (2) are reported. 1 is monomeric, with a terminal PPh2 unit containing a pyramidally coordinated phosphorus atom attached to the four-coordinate metal atom by a Li-P bond of length 2.567(6) Å. 2 crystallizes as dimers, (Me2NCH2CH2NMe2 · LiPPh2)2, with bridging PPh2 units containing (distorted) tetrahedrally coordinated phosphorus atoms: their planar (LiP)2 rings are roughly square-shaped (mean PLiP angle 91°, mean LiP distance 2.61 Å). Discussion of features of these structures is facilitated by ab initio MO calculations on the model systems LiPH2 and (LiPH2)2. Cryoscopic molecular mass measurements and high-field 7Li/31P NMR spectroscopic studies on solutions of 1 and 2 indicate that both solid-state structures are retained in arene solution, though some dissociation of2 into monomers is apparent.

AB - X-ray crystallographic studies on the lithium diphenylphosphide adducts (Me2NCH2CH2)2NMe2 · LiPPh2 ( 1) and Me2NCH2CH2NMe2 · LiPPh2 (2) are reported. 1 is monomeric, with a terminal PPh2 unit containing a pyramidally coordinated phosphorus atom attached to the four-coordinate metal atom by a Li-P bond of length 2.567(6) Å. 2 crystallizes as dimers, (Me2NCH2CH2NMe2 · LiPPh2)2, with bridging PPh2 units containing (distorted) tetrahedrally coordinated phosphorus atoms: their planar (LiP)2 rings are roughly square-shaped (mean PLiP angle 91°, mean LiP distance 2.61 Å). Discussion of features of these structures is facilitated by ab initio MO calculations on the model systems LiPH2 and (LiPH2)2. Cryoscopic molecular mass measurements and high-field 7Li/31P NMR spectroscopic studies on solutions of 1 and 2 indicate that both solid-state structures are retained in arene solution, though some dissociation of2 into monomers is apparent.

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KW - X-ray crystallography

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