TY - JOUR
T1 - Synthesis of Palladium Dimers Bridged by a Range of Phosphinocyclopentadienyl Ligands
AU - Ladipo, Folami T.
AU - Anderson, Gordon K.
AU - Rath, Nigam P.
PY - 1994/12/1
Y1 - 1994/12/1
N2 - The reaction of [PdClMe(cod)] or [Pd2(μ-Cl)2Me2(AsPh3)2] with TlC5H4PPh2 yields the dppcbridged complex [Pd2Me2(μ-η5-C5H4PPh2)2]. The compound crystallizes in the monoclinic space group P21/c with a = 10.511(5) Å, b = 19.848(8) Å, c = 14.933(5) Å, β = 100.31(3)°, V = 3065(2) Å3, and Z = 4. Least-squares refinement converged at R = 0.0468 and Rw = 0.0614, based on 7202 reflections with F > 4.0σ(F). Analogous reactions of [Pd2(μ- Cl)2R2(AsPh3)2] (R = Et, Ph, COMe) with TlC5H4PPh2 generate [Pd2R2(μ-η5-C5H4PPh2)2]. Similarly, dimethylcyclopentadienyl complexes may be prepared by reaction of [Pd2(μ-Cl)2Me2(NC5H3Me2-2,6)] or [Pd2(μ-Cl)2Ph2(AsPh3)2] with TlC5H4PMe2. Reactions of [PdClMe(cod)] with TlC5H4P(OEt)2, or [Pd2(μ-Cl)2Me2(AsPh3)2] with LiC5Me4PPh2, further extend the range of phosphinocyclopentadienyl-bridged palladium complexes. In each case, their NMR spectra indicate that, in contrast to their platinum analogues, they adopt symmetrical, η5 cyclopentadienyl structures in solution. On standing in solution, the compounds [Pd2Me2(μ-η5-C5H4PR2)2] (R = Me, OEt) undergo coupling of the methyl and phosphino groups, and loss of palladium, to yield C5H4PR2Me, each of which has also been prepared from TlC5H4PR2 and iodomethane.
AB - The reaction of [PdClMe(cod)] or [Pd2(μ-Cl)2Me2(AsPh3)2] with TlC5H4PPh2 yields the dppcbridged complex [Pd2Me2(μ-η5-C5H4PPh2)2]. The compound crystallizes in the monoclinic space group P21/c with a = 10.511(5) Å, b = 19.848(8) Å, c = 14.933(5) Å, β = 100.31(3)°, V = 3065(2) Å3, and Z = 4. Least-squares refinement converged at R = 0.0468 and Rw = 0.0614, based on 7202 reflections with F > 4.0σ(F). Analogous reactions of [Pd2(μ- Cl)2R2(AsPh3)2] (R = Et, Ph, COMe) with TlC5H4PPh2 generate [Pd2R2(μ-η5-C5H4PPh2)2]. Similarly, dimethylcyclopentadienyl complexes may be prepared by reaction of [Pd2(μ-Cl)2Me2(NC5H3Me2-2,6)] or [Pd2(μ-Cl)2Ph2(AsPh3)2] with TlC5H4PMe2. Reactions of [PdClMe(cod)] with TlC5H4P(OEt)2, or [Pd2(μ-Cl)2Me2(AsPh3)2] with LiC5Me4PPh2, further extend the range of phosphinocyclopentadienyl-bridged palladium complexes. In each case, their NMR spectra indicate that, in contrast to their platinum analogues, they adopt symmetrical, η5 cyclopentadienyl structures in solution. On standing in solution, the compounds [Pd2Me2(μ-η5-C5H4PR2)2] (R = Me, OEt) undergo coupling of the methyl and phosphino groups, and loss of palladium, to yield C5H4PR2Me, each of which has also been prepared from TlC5H4PR2 and iodomethane.
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U2 - 10.1021/om00024a020
DO - 10.1021/om00024a020
M3 - Article
AN - SCOPUS:0000190335
SN - 0276-7333
VL - 13
SP - 4741
EP - 4745
JO - Organometallics
JF - Organometallics
IS - 12
ER -