528522-58-9Relevant academic research and scientific papers
NCN-pincer metal complexes (Ti, Cr, V, Zr, Hf, and Nb) of the phebox ligand (S,S)-2,6-bis(4′-isopropyl-2′-oxazolinyl)phenyl
Chuchuryukin, Alexey V.,Huang, Rubin,Lutz, Martin,Chadwick, John C.,Spek, Anthony L.,Van Koten, Gerard
, p. 2819 - 2830 (2011)
Reaction of (S,S)-2,6-bis(4′-isopropyl-2′-oxazolinyl) phenyllithium (i-Pr-Phebox-Li) (2a) with 4,4′-bis[P-(chlorogold(I)) diphenylphosphino]biphenyl [(dppbp)(AuCl)2] (5) afforded the new, bimetallic gold complex 4,4′-bis[P-(η1-C-i-Pr
Mono N,C,N-pincer complexes of titanium, vanadium and niobium. Synthesis, structure and catalytic activity in olefin polymerisation
Chuchuryukin, Alexey V.,Huang, Rubin,Van Faassen, Ernst E.,Van Klink, Gerard P. M.,Lutz, Martin,Chadwick, John C.,Spek, Anthony L.,Van Koten, Gerard
, p. 8887 - 8895 (2011/10/09)
Transmetallation of 4,4′-bis{(2,6-bis[(dimethylamino)methyl] phenylgold)diphenyl-phosphino}biphenyl (3) with MCl4 (M = Ti, NbCl, V) in benzene gave the corresponding transition metal pincer complexes (4) and insoluble 4,4′-bis[P-(chloro gold(i))diphenylphosphino]biphenyl (2), which can be quantitatively recovered and recycled. Interestingly, 3 did not react with TiCl3. However, reaction of 2,6-bis[(dimethylamino)methyl] phenyllithium (1) with TiCl3 resulted in formation of the novel diaryltitanium(iv) compound 5 (16% yield), comprising one N,C,N-mer bound NCN-pincer ligand and a second NCN-pincer ligand that is rearranged from a 1,2,6-isomer to a 1,2,4 one. The latter NCN-ligand is dianionic and is bidentate bonded; one of the CH2NMe2 substituents (para to C′ipso) is non-coordinated, while the second CH 2NMe2 group, after C-H activation of one of the Me groups, is η2-C,N-bonded to the titanium centre trans to C ipso of the mer-NCN ligand. The new NCN-pincer metal complexes 2,6-bis[(dimethylamino)methyl]phenylTiCl3 (4a) and 2,6-bis[(dimethylamino)methyl]-phenylVCl2 (4d) gave, after immobilization on MgCl2-based supports, very high activity in ethene polymerisation. The Royal Society of Chemistry 2011.
A new, easily recyclable arylating agent based on a diphosphino-digold(I) complex
Stol, Marianne,Snelders, Dennis J. M.,Kooijman, Huub,Spek, Anthony L.,Van Klink, Gerard P. M.,Van Koten, Gerard
, p. 2589 - 2593 (2008/02/04)
The synthesis of two organogold(i) complexes, [(Au(NCN)) 2(dppbp)] (6) and [(Au(Phebox))2(dppbp)] (9), and their application in subsequent transmetalating reactions are described. A trinuclear organogold(i) complex, [(AuCl)3(tdpppb)] (4) is also reported, which exhibits a surprisingly high solubility in dichloromethane. It was found that 6 and 9 can cleanly transfer the anionic NCN-([C6H3(CH 2NMe2)2-2,6]-) or Phebox-([2,6-bis(oxazolinyl)phenyl]-) moiety to TiIV and PdII centers, respectively. The coproduct [(AuCl)2(dppbp)] (3, dppbp is [4-Ph2PC6H4]2 (1)) formed during this transmetalation reaction, precipitates almost quantitatively from the reaction mixture (toluene) and can thus be separated by simple filtration. In comparison, [AuCl(PPh3)], formed as the coproduct in the transmetalation reaction of [Au(NCN)(PPh3)] with metal salts, has a higher solubility in apolar solvents and thus is more difficult to separate from the resultant organometallic complex. Digold complex 6 has been characterized by NMR spectroscopy and crystallographic analyses. These analyses show that the two gold units are essentially independent. The formation of a dimetallic transmetalating agent based on gold(i) had no effect on its transmetalating properties. The Royal Society of Chemistry 2007.
