14056-91-8Relevant academic research and scientific papers
η5-Cyclopentadienylpalladium(II) complexes: Synthesis, characterization and use for the vinyl addition polymerization of norbornene and the copolymerization with 5-vinyl-2-norbornene or 5-ethylidene-2-norbornene
Blank, Frederik,Vieth, Jana K.,Ruiz, José,Rodríguez, Venancio,Janiak, Christoph
, p. 473 - 487 (2011/02/28)
Dinuclear complexes of palladium(II), containing two bridging halogen (Cl or Br) ligands, [NnBu4]2[(X5C 6)2Pd(μ-Cl)2Pd(C6X 5)2] and [(X5C6)(L)Pd(μ-Y) 2Pd(C6X5)(L)] (X = F, Cl; Y = Cl, Br), readily react with cyclopentadienylthallium, C5H5Tl, to give the corresponding air stable half-sandwich, pseudo-trigonal η5- cyclopentadienylpalladium complexes, [NnBu4] [(η5-C5H5)Pd(C6X 5)2] (X = F 1, Cl 2) and (η5-C 5H5)Pd(C6X5)(L) (X = F, L = CNBut 3, PPh3 4, PMe2Ph 5, PEt3 6, AsPh3 7, SbPh3 8; X = Cl, L = PMe2Ph 9, PEt3 10), respectively. With tetraphenylcyclopentadienylthallium, C5Ph4HTl or pentabenzylcyclopentadienylthallium, C 5Bn5Tl (Bn = CH2Ph) the air stable half-sandwich complexes (η5-C5Ph4H) Pd(C6F5)(AsPh3), 12 and (η5- C5Bn5)Pd(C6F5)(AsPh3), 13 are synthesized accordingly. The molecular structures were verified by NMR-spectroscopy, X-ray crystallography (7, 12, 13) and electron impact-mass spectrometry (EI-MS). The precatalysts 4 and 7 can be activated with methylalumoxane (MAO) for the homopolymerization of norbornene (NB) and 5-ethylidene-2-norbornene (ENB) and for the copolymerization of NB with 5-vinyl-2-norbornene (VNB) or ENB with activities of more than 106 gPNB/(molPd·h). The higher activity of 7/MAO over 4/MAO towards NB homopolymerization was reversed when the olefin-substituted VNB or ENB were added. Then, the more strongly bound PPh3 ligand of 4 (versus AsPh3 of 7) can compete with the olefin functionality of VNB or ENB and assume a directing role for the insertion of the ring double bond. As a consequence 4/MAO shows almost the same activity in NB and ENB homopolymerization.
CATIONIC η5-CYCLOPENTADIENYLPALLADIUM(II) COMPLEXES. COMPOUNDS OF TYPE 5-C5H5)L2>PF6 CONTAINING . TERTIARY PHOSPHINES, ARSINES, AND STIBINES. CRYSTAL AND MOLECULAR STRUCTURE OF η5-CYCLOPENTADIENYLBIS(TRIPHENYLSTIBINE)PALLADIUM(II) HEXAFLUOROPHOSPHATE-DICHLOROMETHANE (1/1)
Roberts, Nicholas K.,Skelton, Brian W.,White, Allan H.,Wild, Stanley, Bruce
, p. 2093 - 2098 (2007/10/02)
The complexes 5-C5H5)L2>PF6 have been prepared in high yield from the appropriate complexes and cyclopentadiene in Me2CO in the presence of AgPF6, or with AgNO3 followed by metathesis with NH4PF6.The brighly coloured compounds condudt as uni-univalent electrolytes in Me2CO and CH2Cl2 and have spectroscopic properties consistent with η5 co-ordination of the cyclopentadienyl moiety in solution.The molecular structure of 5-C5H5)(SbPh3)2>PF6*CH2Cl2 has been determined by a single crystal X-ray analysis.The crystals are monoclinic, space group P21/c with a=12.506(6), b=19.002(7), c=18.575(5) Angstoem, β=106.53(3) deg, and Z=4.The structure was solved by heavy-atom methods at 295(1) K and refined by least-squares methods to R=0.051 for 4383 observed reflections.The arrangement of two antimony atoms and the centre of the cyclopentadienyl ring about the palladium atom is approximately trigonal.The co-ordinated cyclopentadienyl moiety shows no significant deviations from planarity.
Inorganic linkage isomerism of the thiocyanate ion
Burmeister, John L.,Basolo, Fred
, p. 1587 - 1593 (2008/10/08)
Linkage isomers of metal complexes of the type M-SCN (thiocyanato) and M-NCS (isothiocyanato) are reported for the compounds [Pd(As(C6H5)3)2X2] and [Pd(bipy)X2]. The method of preparation d
