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The in situ generation of 3-diazonium cations from 3-aminopyridine and their subsequent stability under experimental conditions used for electrografting of pyridine groups were investigated by spectroscopy and electrochemistry. UV spectroscopy revealed the rapid kinetics for the reaction of 3-aminopyridine with sodium nitrite in HCl to form the(More)
A force field model for ansa-zirconocene complexes is constructed, which represents each C atom of the C 5-ring ligands as being bonded directly to the metal center, rather than by way of the C 5-ring centroids. This h 5-model, which describes coordination geometries by mutual repulsions of the C 5-ring and halide ligands, has no adjustable equilibrium or(More)
Cu(OiPr)2 was reacted with several β-diketimine ligands, nacnac(R)H. Sterically undemanding ligands with N-benzyl substituents afforded the dimeric heteroleptic complexes [nacnac(Bn)Cu(μ-OiPr)]2 and [3-Cl-nacnac(Bn)Cu(μ-OiPr)]2 (Bn = benzyl). With sterically more demanding amines, dimerization was not possible, and the putative nacnacCuOiPr intermediate(More)
The reaction of N,N'-dibenzyl-2-amino-4-imino-pent-2-ene, nacnac(Bn)H, with 1 or 2 equiv. of MgnBu₂ afforded the homoleptic complex nacnac(Bn)₂Mg. The reaction of nacnac(Bn)H with Mg(N(SiMe₃)₂)₂ yielded nacnac(Bn)MgN(SiMe₃)₂, which reacted with tert-butanol to form nacnac(Bn)MgOtBu. The latter complex crystallizes as an alkoxide bridge dimer and is active(More)
The ring-bridged chromocene carbonyl complex Me z Si(C sMe 4)zCr(CO) 1 is obtained by reaction of Me~ Si(C, MC 4)2 Li ~ with CrCl z. THF in the presence of CO. Reaction with CO transforms the monocarbonyl complex 1 to a dicarbonyl complex MezSi(CsMe4)(Cs(endo-3-H)(2-CHz)Me3)Cr(CO)2 2; in this reaction, a hydrogen atom is shifted from one of the cx-CH 3(More)
Diiminopyrrolide copper alkoxide complexes, LCuOR (OR(1)=N,N-dimethylamino ethoxide, OR(2)=2-pyridyl methoxide), are active for the polymerization of rac-lactide at ambient temperature in benzene to yield polymers with M(w)/M(n)=1.0-1.2. X-ray diffraction studies showed bridged dinuclear complexes in the solid state for both complexes. While LCuOR(1)(More)
Ligands in which multiple metal-binding domains are linked by a metal-containing moiety rather than a conventional organic group are described as "expanded ligands". The use of 4,4'-difunctionalised {Ru(tpy)(2)} units provides a linear spacer between metal-binding domains and we have extended this motif to expanded ligands containing two carboxylic acid(More)
Diketimine ligands bearing N-benzyl, N-9-anthrylmethyl and N-mesitylmethyl substituents (nacnac(Bn)H, nacnac(An)H, and nacnac(Mes)H) were prepared from condensation of the amine with either acetyl acetone or its ethylene glycol monoketal. Chlorination with N-chlorosuccinimide in the 3-position yielded Clnacnac(Bn)H and Clnacnac(An)H. The ligands were(More)
Manganese(III) complexes of tetradentate diphenolate-diamino (NNOO(2-)) ligands were prepared from aerobic reaction of MnCl2 with the respective ligands in basic methanolic solution. Methoxide complexes (NNOO)Mn(OMe)(MeOH)0-1 were obtained for three ligands, while others only provided the respective chloride complexes (NNOO)Mn(Cl)(MeOH). Complexes were(More)