Distortion of cyclopentadienyl rings in .ETA.5-cyclopentadienyl-palladium complexes: crystal structures of [Pd(C5H5)Cl(PMe2Ph)] and [Pd(C5H5)(Ph2PCH2CH2PPh2)][PF6]

R J CROSS, R W HOYLE, A R KENNEDY, L MANOJLOVICMUIR, K W MUIR

Research output: Contribution to journalArticle

Abstract

The structures of [Pd(C5H5)Cl(PMe2Ph)] and [Pd(C5H5)(dppe)]PF6 (dppe = Ph2PCH2CH2PPh2) have been determined by X-ray analysis. Both are eta5-cyclopentadienyl compounds, with the Cp ring nearly perpendicular to the PdPCl or PdP2 plane. Comparison of their molecular geometries with those of other cyclopentadienyl-palladium complexes of the types PdCpLL' and PdCpL2 reveals the existence of a complete range of ring-PdLL' or ring-PdL2 orientations and suggests that the usual assignment of structures of these types as either staggered or eclipsed is not realistic. Likewise, the patterns of long and short C-C bonds of the Cp rings do not in general follow the sequences expected for the idealized geometries, although large librational distortions of the C5H5 rings in most of the compounds limit the accuracy of these determinations. The lengths of the Pd-C(Cp) bonds appear to be much more dependent on the relative trans influences of L and L' than on the ring orientations.

LanguageEnglish
Pages265-271
Number of pages7
JournalJournal of Organometallic Chemistry
Volume468
Issue number1-2
Publication statusPublished - 5 Apr 1994

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Palladium
palladium
Crystal structure
X-Rays
crystal structure
Geometry
rings
X ray analysis
geometry
x rays

Keywords

  • palladium
  • cyclopentadiadienyl
  • x-ray diffraction
  • molecular structure
  • prganometallic complexes

Cite this

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title = "Distortion of cyclopentadienyl rings in .ETA.5-cyclopentadienyl-palladium complexes: crystal structures of [Pd(C5H5)Cl(PMe2Ph)] and [Pd(C5H5)(Ph2PCH2CH2PPh2)][PF6]",
abstract = "The structures of [Pd(C5H5)Cl(PMe2Ph)] and [Pd(C5H5)(dppe)]PF6 (dppe = Ph2PCH2CH2PPh2) have been determined by X-ray analysis. Both are eta5-cyclopentadienyl compounds, with the Cp ring nearly perpendicular to the PdPCl or PdP2 plane. Comparison of their molecular geometries with those of other cyclopentadienyl-palladium complexes of the types PdCpLL' and PdCpL2 reveals the existence of a complete range of ring-PdLL' or ring-PdL2 orientations and suggests that the usual assignment of structures of these types as either staggered or eclipsed is not realistic. Likewise, the patterns of long and short C-C bonds of the Cp rings do not in general follow the sequences expected for the idealized geometries, although large librational distortions of the C5H5 rings in most of the compounds limit the accuracy of these determinations. The lengths of the Pd-C(Cp) bonds appear to be much more dependent on the relative trans influences of L and L' than on the ring orientations.",
keywords = "palladium, cyclopentadiadienyl, x-ray diffraction, molecular structure, prganometallic complexes",
author = "CROSS, {R J} and HOYLE, {R W} and KENNEDY, {A R} and L MANOJLOVICMUIR and MUIR, {K W}",
year = "1994",
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pages = "265--271",
journal = "Journal of Organometallic Chemistry",
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Distortion of cyclopentadienyl rings in .ETA.5-cyclopentadienyl-palladium complexes: crystal structures of [Pd(C5H5)Cl(PMe2Ph)] and [Pd(C5H5)(Ph2PCH2CH2PPh2)][PF6]. / CROSS, R J ; HOYLE, R W ; KENNEDY, A R ; MANOJLOVICMUIR, L ; MUIR, K W .

In: Journal of Organometallic Chemistry, Vol. 468, No. 1-2, 05.04.1994, p. 265-271.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Distortion of cyclopentadienyl rings in .ETA.5-cyclopentadienyl-palladium complexes: crystal structures of [Pd(C5H5)Cl(PMe2Ph)] and [Pd(C5H5)(Ph2PCH2CH2PPh2)][PF6]

AU - CROSS, R J

AU - HOYLE, R W

AU - KENNEDY, A R

AU - MANOJLOVICMUIR, L

AU - MUIR, K W

PY - 1994/4/5

Y1 - 1994/4/5

N2 - The structures of [Pd(C5H5)Cl(PMe2Ph)] and [Pd(C5H5)(dppe)]PF6 (dppe = Ph2PCH2CH2PPh2) have been determined by X-ray analysis. Both are eta5-cyclopentadienyl compounds, with the Cp ring nearly perpendicular to the PdPCl or PdP2 plane. Comparison of their molecular geometries with those of other cyclopentadienyl-palladium complexes of the types PdCpLL' and PdCpL2 reveals the existence of a complete range of ring-PdLL' or ring-PdL2 orientations and suggests that the usual assignment of structures of these types as either staggered or eclipsed is not realistic. Likewise, the patterns of long and short C-C bonds of the Cp rings do not in general follow the sequences expected for the idealized geometries, although large librational distortions of the C5H5 rings in most of the compounds limit the accuracy of these determinations. The lengths of the Pd-C(Cp) bonds appear to be much more dependent on the relative trans influences of L and L' than on the ring orientations.

AB - The structures of [Pd(C5H5)Cl(PMe2Ph)] and [Pd(C5H5)(dppe)]PF6 (dppe = Ph2PCH2CH2PPh2) have been determined by X-ray analysis. Both are eta5-cyclopentadienyl compounds, with the Cp ring nearly perpendicular to the PdPCl or PdP2 plane. Comparison of their molecular geometries with those of other cyclopentadienyl-palladium complexes of the types PdCpLL' and PdCpL2 reveals the existence of a complete range of ring-PdLL' or ring-PdL2 orientations and suggests that the usual assignment of structures of these types as either staggered or eclipsed is not realistic. Likewise, the patterns of long and short C-C bonds of the Cp rings do not in general follow the sequences expected for the idealized geometries, although large librational distortions of the C5H5 rings in most of the compounds limit the accuracy of these determinations. The lengths of the Pd-C(Cp) bonds appear to be much more dependent on the relative trans influences of L and L' than on the ring orientations.

KW - palladium

KW - cyclopentadiadienyl

KW - x-ray diffraction

KW - molecular structure

KW - prganometallic complexes

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EP - 271

JO - Journal of Organometallic Chemistry

T2 - Journal of Organometallic Chemistry

JF - Journal of Organometallic Chemistry

SN - 0022-328X

IS - 1-2

ER -