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The influence of metal coordination on ligand geometry: the structure of 2-(diphenylphosphino)acetophenone and bis(2-(diphenylphosphino)acetophenone)palladium(II)bistriflate

Johansson, Maria LU ; Andersson, Carlaxel LU and Oskarsson, Åke LU (2002) In Journal of Molecular Structure 606(1-3). p.51-59
Abstract
The structures of 2(diphenylphosphino)acetophenone and bis(2(diphenyl phosphino)acetophenone)palladium(II)bistriflate have been determined by X-ray crystallography. The ligand is of interest because its P,O donor set combines the hard and soft properties. In the Pd-complex, which was prepared by treating tetrakisacetonitrile-palladium-bistriflate with 2-(diphenylphosphino)acetophenone in dichloromethane for 4 h at room temperature, the O-coordination provides a masked coordinative unsaturation. The ligand crystallises in the monoclinic space group P2(1)/c with cell dimensions a = 11.050(2), b = 16.052(3), c = 9.7082(19) Angstrom, beta = 109.58(3)degrees, V = 1622.4(6) Angstrom(3) and Z = 4, synchrotron radiation, lambda = 0.8520 Angstrom.... (More)
The structures of 2(diphenylphosphino)acetophenone and bis(2(diphenyl phosphino)acetophenone)palladium(II)bistriflate have been determined by X-ray crystallography. The ligand is of interest because its P,O donor set combines the hard and soft properties. In the Pd-complex, which was prepared by treating tetrakisacetonitrile-palladium-bistriflate with 2-(diphenylphosphino)acetophenone in dichloromethane for 4 h at room temperature, the O-coordination provides a masked coordinative unsaturation. The ligand crystallises in the monoclinic space group P2(1)/c with cell dimensions a = 11.050(2), b = 16.052(3), c = 9.7082(19) Angstrom, beta = 109.58(3)degrees, V = 1622.4(6) Angstrom(3) and Z = 4, synchrotron radiation, lambda = 0.8520 Angstrom. The Pd-complex crystallises in the orthorhombic space group P2(1)2(1)2(1) with cell dimensions a = 11.867(2), b = 18.162(4), c = 19.603(4) Angstrom, V 4224 9(15) Angstrom(3) and Z = 4, MoKalpha radiation. Both structures were solved by direct methods and the refinements resulted in the R-values of 0.059 and 0.043, for the organic compound and the palladium compound, respectively. Two bi-dentate ligand binds to palladium(II) in a cis-configuration. The Pd-O distances are 2.060(3) and 2.096(2) Angstrom and the Pd-P distances 2.2290(10) and 2.2294(10) Angstrom, showing a large trans-influence of the phosphorus atoms. Half-normal probability plot analyses indicate that the s.u.'s are largely underestimated in the investigated structures. The bond-angles around the phosphorus atom and the orientation of the keto-substituted phenyl rings as well as the orientation of the keto-groups are highly affected by metal complexation. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
X-ray crystallography, palladium(II), half-normal probability plot, analysis
in
Journal of Molecular Structure
volume
606
issue
1-3
pages
51 - 59
publisher
Elsevier
external identifiers
  • wos:000174334700006
  • scopus:0037181393
ISSN
0022-2860
DOI
10.1016/S0022-2860(01)00861-4
language
English
LU publication?
yes
id
8a02f0a6-5f03-497d-8307-ae7276f38fe3 (old id 342020)
date added to LUP
2007-10-30 14:28:55
date last changed
2017-01-01 07:21:49
@article{8a02f0a6-5f03-497d-8307-ae7276f38fe3,
  abstract     = {The structures of 2(diphenylphosphino)acetophenone and bis(2(diphenyl phosphino)acetophenone)palladium(II)bistriflate have been determined by X-ray crystallography. The ligand is of interest because its P,O donor set combines the hard and soft properties. In the Pd-complex, which was prepared by treating tetrakisacetonitrile-palladium-bistriflate with 2-(diphenylphosphino)acetophenone in dichloromethane for 4 h at room temperature, the O-coordination provides a masked coordinative unsaturation. The ligand crystallises in the monoclinic space group P2(1)/c with cell dimensions a = 11.050(2), b = 16.052(3), c = 9.7082(19) Angstrom, beta = 109.58(3)degrees, V = 1622.4(6) Angstrom(3) and Z = 4, synchrotron radiation, lambda = 0.8520 Angstrom. The Pd-complex crystallises in the orthorhombic space group P2(1)2(1)2(1) with cell dimensions a = 11.867(2), b = 18.162(4), c = 19.603(4) Angstrom, V 4224 9(15) Angstrom(3) and Z = 4, MoKalpha radiation. Both structures were solved by direct methods and the refinements resulted in the R-values of 0.059 and 0.043, for the organic compound and the palladium compound, respectively. Two bi-dentate ligand binds to palladium(II) in a cis-configuration. The Pd-O distances are 2.060(3) and 2.096(2) Angstrom and the Pd-P distances 2.2290(10) and 2.2294(10) Angstrom, showing a large trans-influence of the phosphorus atoms. Half-normal probability plot analyses indicate that the s.u.'s are largely underestimated in the investigated structures. The bond-angles around the phosphorus atom and the orientation of the keto-substituted phenyl rings as well as the orientation of the keto-groups are highly affected by metal complexation.},
  author       = {Johansson, Maria and Andersson, Carlaxel and Oskarsson, Åke},
  issn         = {0022-2860},
  keyword      = {X-ray crystallography,palladium(II),half-normal probability plot,analysis},
  language     = {eng},
  number       = {1-3},
  pages        = {51--59},
  publisher    = {Elsevier},
  series       = {Journal of Molecular Structure},
  title        = {The influence of metal coordination on ligand geometry: the structure of 2-(diphenylphosphino)acetophenone and bis(2-(diphenylphosphino)acetophenone)palladium(II)bistriflate},
  url          = {http://dx.doi.org/10.1016/S0022-2860(01)00861-4},
  volume       = {606},
  year         = {2002},
}