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Synthesis and Characterization of Constrained Geometry Oxygen and Sulphur Functionalized Cyclopentadienylchromium Complexes and Their Use in Catalysis for Olefin Polymerization.
Molecules
May 2017
The Laboratory of Organometallic Chemistry, East China University of Science and Technology, Shanghai 200237, China.
A series of constrained geometry O-functionalized cyclopentadienylchromium complexes (-) and a S-functionalized cyclopentadienylchromium complex () were first synthesized, characterized, and tested as catalyst precursors for the olefin polymerization. In the presence of MAO, the complexes exhibited high catalytic activity for the polymerization of ethylene. It is shown that ligand variations can have a substantial effect on catalyst activity and stability.
View Article and Find Full Text PDFNickelacyclopentadienylchromium tricarbonyl unit as a bulky pseudohalogen in cyclopentadienylchromium complexes leading to low-energy high-spin structures.
Inorg Chem
June 2015
‡Department of Chemistry and Center for Computational Chemistry, University of Georgia, Athens, Georgia 30602, United States.
Recent studies, particularly from the laboratory of Buchalski and co-workers, have resulted in the syntheses of nickelacyclopentadienyl and nickelafluorenyl metallacycles that can function as pentahapto ligands in transition-metal complexes, similar to the ubiquitous cyclopentadienyl ligand. The structures and energetics of the neutral binuclear chromium carbonyls (CpNiC4H4)2Cr2(CO)n (n = 6, 5, 4, 3; Cp = η(5)-C5H5) containing the unsubstituted nickelacyclopentadienyl ligand have been investigated by density functional theory. The lowest energy (CpNiC4H4)2Cr2(CO)n (n = 6, 4) structures are similar to the corresponding experimentally characterized Cp2Cr2(CO)n structures with predicted Cr-Cr distances of ∼3.
View Article and Find Full Text PDFCyclopentadienylchromium complexes of 1,2,3,5-dithiadiazolyls: eta2pi complexes of cyclic sulfur-nitrogen compounds.
Angew Chem Int Ed Engl
July 2006
Department of Chemistry, National University of Singapore, Kent Ridge 119260, Singapore.
Heterocyclic thionates as a new class of bridging ligands in oxo-centered triangular cyclopentadienylchromium(III) complexes.
Inorg Chem
July 2005
Department of Chemistry, National University of Singapore, Kent Ridge, Singapore 117543.
The interactions of the benzothiazolate complex, CpCr(CO)(2)(SCSN(C(6)H(4))) (2), and the tetrazole thiolate complex, CpCr(CO)(3)(eta(1)-SCN(4)Ph) (3), with controlled amounts of Me(3)OBF(4) and (MeO)(2)SO(2), respectively, produced the corresponding mu(3)-oxo trinuclear thionate-bridged complexes, [Cp(3)Cr(3)(mu(2)-OH)(mu(3)-O)(mu(2)-eta(2)-SCSN(C(6)H(4)))(2)](5)BF(4) (45%) and [Cp(3)Cr(3)(mu(2)-OH)(mu(3)-O)(mu(2)-eta(2)-SCN(4)Ph)(2)](9)(MeOSO(3)) (53%), together with their respective free dimethylated thiolate ligands, [MeSCSNMe(C(6)H(4))](4)BF(4) and (Me(2)SCN(4)Ph)(8)MeOSO(3). The reaction of 3 with Me(3)OBF(4) resulted in the isolation of a binuclear complex, [Cp(2)Cr(2)(mu-OH)(mu-eta(2)-SCN(4)Ph)(2)](7)BF(4) (43%), and (8)BF(4) (27%). The reaction of the thiopyridine complex, CpCr(CO)(2)(SPy) (4), with I(2) also produced a similar mu(3)-oxo complex 10 (31%), together with CpCrI(2)(THF) (11) and the disulfide (SPy)(2).
View Article and Find Full Text PDFHomolytic cleavage and aggregation processes in cyclopentadienylchromium chemistry.
Acc Chem Res
March 2004
Department of Chemistry, National University of Singapore, Kent Ridge, Singapore 119260.
The reactivity of the cyclopentadienylchromium tricarbonyl dimer [CpCr(CO)3]2 (Cp = C5H5, 1) toward several classes of organo-P-, -S- and -N-compounds will be described. The organic substrates include the following: (i) bis(diphenylthiophosphinyl)disulfane, R2P(S)SSP(S)R2; (ii) bis(thiophosphoryl)disulfane, (RO)2P(S)SSP(S)(OR)2; (iii) tetraalkylthiuram disulfides, R2NC(S)SSC(S)NR2; (iv) tetraalkyldiphosphine disulfides, R2P(S)P(S)R2; (v) dibenzothiazolyl disulfide, (C6H4NSC)2; and (vi) Lawesson's reagent, (CH3OC6H4)2P2S4. The primary products, namely, the complexes CpCr(CO)2(SPR2), CpCr(CO)2)(S2CNR2), CpCr(CO)2(SCSN(C6H4)), and CpCr(CO)2(SPC6H4OCH3), containing the thiophosphinito, dithiocarbamate, 2-mercaptobenzothiazole, and dithiophosphorane ligands, respectively, arise from facile cleavage of the S-S, P-P, and P-S bonds in the organic substrates.
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