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The influence of metal coordination on ligand geometry: the structure of N-t-butyl-2-(diphenylphosphino)benzylammoniumchloride and (N-t-butyl-2-(diphenylphosphino)benzylamine)diacetatepalladium(II)

Johansson, Maria LU ; Andersson, Carlaxel LU and Oskarsson, Åke LU (2002) In Journal of Molecular Structure 608(2-3). p.219-228
Abstract
The structures of N-t-butyl-2-(diphenylphosphino)benzylammoniumchloride and N-t-butyl-2-(diphenylphosphino)benzylaminediacetatepalladium(II) have been determined by X-ray crystallography. The Pd-complex was prepared by treating palladiumdiacetate with N-t-butyl-2-(diphenylphosphino)benzylamine in CH2Cl2 for 4 h at room temperature. The organic compound crystallises in the monoclinic space group P2(1)/c with cell dimensions a = 13.664(3), b = 15.635(3), c = 10.408(2) Angstrom, beta = 100.14(3)degrees, V = 2188.7(8) Angstrom(3) and Z = 4, synchrotron radiation, lambda = 0.9836 Angstrom. The Pd-compound crystallises in the orthorhombic space group Pna2(1) with cell dimensions a = 15.444(3), b = 13.233(3), c = 12.730(3) Angstrom, V = 2601.6(9)... (More)
The structures of N-t-butyl-2-(diphenylphosphino)benzylammoniumchloride and N-t-butyl-2-(diphenylphosphino)benzylaminediacetatepalladium(II) have been determined by X-ray crystallography. The Pd-complex was prepared by treating palladiumdiacetate with N-t-butyl-2-(diphenylphosphino)benzylamine in CH2Cl2 for 4 h at room temperature. The organic compound crystallises in the monoclinic space group P2(1)/c with cell dimensions a = 13.664(3), b = 15.635(3), c = 10.408(2) Angstrom, beta = 100.14(3)degrees, V = 2188.7(8) Angstrom(3) and Z = 4, synchrotron radiation, lambda = 0.9836 Angstrom. The Pd-compound crystallises in the orthorhombic space group Pna2(1) with cell dimensions a = 15.444(3), b = 13.233(3), c = 12.730(3) Angstrom, V = 2601.6(9) Angstrom(3) and Z = 4, Mo Kalpha radiation. Both structures were solved by direct methods and the refinements resulted in the R-values 0.080 and 0.037, respectively. N-t-butyl-2-(diphenylphosphino)benzylammoniumchloride has an extensive hydrogen bonding with two bridging Cl- between the ammonium groups from two different organic ligands. The bi-dentate ligand binds to palladium(II) via both phosphorus and nitrogen, while two acetate bind via one of their oxygens forming a pseudo square-planar coordination around palladium. The Pd-N distance is 2.075(3) Angstrom, Pd-P = 2.2133(9) Angstrom and the Pd-O distances are 2.041(3) Angstrom (trans to N) and 2.092(2) Angstrom (trans to P). Half-normal probability plot analysis indicates that the s.u,.'s are underestimated in at least one of the investigated structures. Complexation with palladium influences torsion-angles in the amine side-chain in N-t-butyl-2-(diphenylphosphino)benzylamine as well as bond-angles around the N and P atoms, clearly a consequence of the formation of the chelate, while the crystal packing influences the orientation of the phenyl rings. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
keywords
half-normal probability plot, X-ray crystallography, palladium(II), analysis, synchrotron radiation, catalysis
in
Journal of Molecular Structure
volume
608
issue
2-3
pages
219 - 228
publisher
Elsevier
external identifiers
  • wos:000174677600013
  • scopus:0037157214
ISSN
0022-2860
DOI
10.1016/S0022-2860(01)00958-9
language
English
LU publication?
yes
id
acb9e3c5-8fef-4888-bc5b-e125322d708d (old id 341071)
date added to LUP
2007-10-29 15:51:47
date last changed
2017-01-01 07:07:14
@article{acb9e3c5-8fef-4888-bc5b-e125322d708d,
  abstract     = {The structures of N-t-butyl-2-(diphenylphosphino)benzylammoniumchloride and N-t-butyl-2-(diphenylphosphino)benzylaminediacetatepalladium(II) have been determined by X-ray crystallography. The Pd-complex was prepared by treating palladiumdiacetate with N-t-butyl-2-(diphenylphosphino)benzylamine in CH2Cl2 for 4 h at room temperature. The organic compound crystallises in the monoclinic space group P2(1)/c with cell dimensions a = 13.664(3), b = 15.635(3), c = 10.408(2) Angstrom, beta = 100.14(3)degrees, V = 2188.7(8) Angstrom(3) and Z = 4, synchrotron radiation, lambda = 0.9836 Angstrom. The Pd-compound crystallises in the orthorhombic space group Pna2(1) with cell dimensions a = 15.444(3), b = 13.233(3), c = 12.730(3) Angstrom, V = 2601.6(9) Angstrom(3) and Z = 4, Mo Kalpha radiation. Both structures were solved by direct methods and the refinements resulted in the R-values 0.080 and 0.037, respectively. N-t-butyl-2-(diphenylphosphino)benzylammoniumchloride has an extensive hydrogen bonding with two bridging Cl- between the ammonium groups from two different organic ligands. The bi-dentate ligand binds to palladium(II) via both phosphorus and nitrogen, while two acetate bind via one of their oxygens forming a pseudo square-planar coordination around palladium. The Pd-N distance is 2.075(3) Angstrom, Pd-P = 2.2133(9) Angstrom and the Pd-O distances are 2.041(3) Angstrom (trans to N) and 2.092(2) Angstrom (trans to P). Half-normal probability plot analysis indicates that the s.u,.'s are underestimated in at least one of the investigated structures. Complexation with palladium influences torsion-angles in the amine side-chain in N-t-butyl-2-(diphenylphosphino)benzylamine as well as bond-angles around the N and P atoms, clearly a consequence of the formation of the chelate, while the crystal packing influences the orientation of the phenyl rings.},
  author       = {Johansson, Maria and Andersson, Carlaxel and Oskarsson, Åke},
  issn         = {0022-2860},
  keyword      = {half-normal probability plot,X-ray crystallography,palladium(II),analysis,synchrotron radiation,catalysis},
  language     = {eng},
  number       = {2-3},
  pages        = {219--228},
  publisher    = {Elsevier},
  series       = {Journal of Molecular Structure},
  title        = {The influence of metal coordination on ligand geometry: the structure of N-t-butyl-2-(diphenylphosphino)benzylammoniumchloride and (N-t-butyl-2-(diphenylphosphino)benzylamine)diacetatepalladium(II)},
  url          = {http://dx.doi.org/10.1016/S0022-2860(01)00958-9},
  volume       = {608},
  year         = {2002},
}