PubMed Health⌕ Search

Biomedical subjects

Vernon C Gibson

Publications and source records attributed to Vernon C Gibson.

At least 19 recordsLinked to original sources
PubMed2006

Synthesis and structures of bimetallic and polymeric zinc coordination compounds supported by salicylaldiminato and anilido-aldimine ligands.

A series of bimetallic zinc complexes bearing salicylaldiminato (1b-3b) or anilido-aldimine (4c-5c) ligand frameworks, in which the metal centres are separated by aliphatic spacer groups containing 3-6 methylene units, were targeted. X-Ray analysis of salicylaldiminato derivative 2b, with a 4 carbon spacer group, revealed a coordination polymer in the solid state where each zinc centre is ligated by two salicylaldiminato ligands. Contrastingly, the structure of the anilido-aldimine complex 4c, with a 3 carbon methylene spacer group, was found to be a discrete bimetallic complex. These differences are attributed to the differing steric protection at the anilido vs phenoxy donors, the latter more readily facilitating bridges between metal centres.

Journal Article↗
PubMed2006

Group 4 catalysts for ethene polymerization containing tetradentate salicylaldiminato ligands.

The structural properties of three new classes of titanium and zirconium complex bearing tetradentate salicylaldiminato proligands are elucidated using X-ray diffraction and NMR spectroscopy. On activation with MAO co-catalyst, their behaviour in ethene polymerization depends strongly on the nature of the structure and the substitution pattern. One titanium complex based on a 2-aminobenzylamine (C3-chain) backbone has a trans arrangement of the co-ligand sites and, unsurprisingly, does not polymerize ethene. The 1,8-diaminonaphthalene (C3-chain) backbone gives a rather ring-strained cis complex, but was also unproductive. A range of cis complexes of zirconium with the 2,2'-diaminobibenzyl (C6-chain) backbone give low to moderate productivities of multimodal poly(ethene), while in contrast the structurally analogous titanium compounds provide highly active, single site catalysts. Thermal degradation of these catalysts is slowed significantly by a substitution pattern on the phenolate unit which sterically protects the imine donor unit; a phenomenon which has been previously observed in much lower activity catalysts based on 2,2'-diaminobiphenyl (C4-chain) but which does not improve the stability of the very highly active unbridged systems.

Journal Article↗
PubMed2006

Study of ligand substituent effects on the rate and stereoselectivity of lactide polymerization using aluminum salen-type initiators.

A series of aluminum salen-type complexes [where salen is N,N'-bis(salicylaldimine)-1,2-ethylenediamine] bearing ligands that differ in their steric and electronic properties have been synthesized and investigated for the polymerization of rac-lactide. X-ray crystal structures on key precatalysts reveal metal coordination geometries intermediate between trigonal bipyramidal and square-based pyramidal. Both the phenoxy substituents and the backbone linker have a significant influence over the polymerization. Electron-withdrawing groups attached to the phenoxy donor generally gave an increased polymerization rate, whereas large ortho substituents generally slowed down the polymerization. The vast majority of the initiators afforded polylactide with an isotactic bias; only one exhibited a bias toward heteroselectivity. Isoselectivity generally increases with increased flexibility of the backbone linker, which is presumed to be better able to accommodate any potential steric clashes between the propagating polymer chain, the inserting monomer unit, and the substituents on the phenoxy donor.

Aluminum↗
PubMed2006

Coordination complexes bearing potentially tetradentate phenoxyamine ligands.

A series of metal complexes containing potentially tetradentate phenoxyamine ligands is described. The ligands are found to bind to main-group metals and first-row transition-metal centres with variable denticity depending upon the requirements of the particular metal centre. Bidentate [Al(III)], tridentate [Mg(II), Ca(II), Zn(II)] and tetradentate [K(I), Cr(III), Fe(II), Co(II)] binding modes have been established unambiguously through single-crystal X-ray structure determinations.

Journal Article↗
PubMed2006

Synthetic, structural, mechanistic, and computational studies on single-site beta-diketiminate tin(II) initiators for the polymerization of rac-lactide.

A family of tin(II) complexes supported by beta-diketiminate ligands has been investigated as initiators for the polymerization of rac-lactide. Kinetic studies reveal a first-order dependence on [lactide], but with a significant induction period. Linear plots of M(n) versus conversion and [M](o)/[I](o) versus conversion, along with narrow molecular weight distributions (typically 1.07-1.10), are indicative of well-controlled, "living" polymerizations. Less sterically hindered derivatives promote faster propagation than their bulky analogues, in accord with a more accessible active site. Enhanced rates of polymerization are observed for ligands bearing halogenated N-aryl substituents, a consequence of the more Lewis acidic nature of the Sn(II) centers. All of the initiators exhibit a similar bias toward heterotactic polylactide, which is attributed to a chain-end control mechanism influenced predominantly by the presence of the Sn 5s(2) lone pair of electrons rather than the steric or electronic properties of the beta-diketiminate ligand. The tin(II) isopropyl-(S)-lactate complex, ((Me)BDI(DIPP))SnOCH(Me)COO(i)Pr (14), has been synthesized as a model compound for the propagating species by treatment of ((Me)BDI(DIPP))Sn(NMe(2)) with isopropyl-(S)-lactate. An X-ray structure determination showed that the lactate ligand forms a five-membered chelate ring with a weak donor bond from the carbonyl oxygen atom to the tin center. A B3LYP density functional computational study indicates that insertion of the first lactide monomer into the tin(II) alkoxide bond is facile, with the induction period arising from a slower insertion of the second (and possibly third and fourth) monomer units.

Crystallography, X-Ray↗
PubMed2006

An unprecedented alpha-olefin distribution arising from a homogeneous ethylene oligomerization catalyst.

Treatment of the bis(benzimidazolyl)amine chromium complex 2 with ethylene in the presence of MAO affords an exceptionally active oligomerization catalyst and an unprecedented distribution of 1-olefin products in which the C4n series is much more abundant than the C4n+2 series. Deuterium labeling studies are consistent with a metallacyclic chain growth mechanism in which the unusual product distribution arises from the interplay of two sites.

Journal Article↗
PubMed2006

Redox control within single-site polymerization catalysts.

The activity of a single-site titanium-based lactide polymerization initiator supported by a ferrocenyl-derivatized salen ligand is shown to be modulated by a chemical redox switch; a substantially higher rate of propagation is found for the neutral catalyst compared to its oxidized dicationic ferrocenium counterpart.

Journal Article↗
PubMed2006

New S/O-substituted ferrocenediyl ligands and their metal complexes.

New unsymmetrical S/O 1,1'-disubstituted ferrocenediyl ethers and hydroxides have been synthesised. The coordination chemistry of 1-(methylsulfanyl)-1'-(methoxy)ferrocene has been investigated with palladium(II) and platinum(II) precursors. With palladium(II), a bis-mu-chloro-bridged dimeric complex was obtained with the ligand bound solely through the thioether donor group. With platinum(II), a bis-ligand trans-sulfur ligated complex was obtained and structurally characterised.

Journal Article↗
PubMed2006

Titanium-salen complexes as initiators for the ring opening polymerisation of rac-lactide.

A family of bis(iso-propoxide) titanium(IV) complexes supported by tetradentate Schiff base (salen) ligands has been synthesised and characterised, including a structural determination of N,N'-bis(6'-methylenimino-2',4'-di-tert-butylphenoxy)cyclohexyl-(1R,2R)-diamino titanium(IV) bis(iso-propoxide). Their suitability for initiating the ring-opening polymerisation of rac-lactide has been investigated. Polymerisation activities are shown to correlate with the electronic properties of the substituents within the salen ligand. In contrast to aluminium-salen initiators, electron-withdrawing substituents on the Schiff base ligand have a detrimental influence upon polymerisation activities, whereas the use of electron-donating alkoxy-functionalized ligands has allowed the highest recorded activity to date for a titanium-based initiator.

Journal Article↗
PubMed2005

Discovery and optimization of new chromium catalysts for ethylene oligomerization and polymerization aided by high-throughput screening.

High throughput screening (HTS) of a 205 member Schiff base salicylaldimine ligand library derived from salicylaldehydes bearing bulky ortho-substituents, i.e., 9-anthracenyl, 1,4,5,8-tetramethylanthracenyl or triptycenyl, reacted in-situ with (p-tolyl)CrCl2(thf)3, identified two new classes of highly active chromium based systems for the oligomerization and polymerization of ethylene, respectively. The polymerization system comprises bidentate ortho-substituted anthracenyl Schiff bases bearing small primary or secondary alkyl imine substituents. The oligomerization catalysts are based upon tridentate ortho-triptycenyl-substituted Schiff bases with pyridylmethyl or quinolyl substituents. Validation tests confirmed polymerization productivities of up to 3000 g x mmol(-1)h(-1)bar(-1) for the polymerization catalyst systems while the oligomerization catalysts gave productivities up to 10 000 g x mmol(-1)h(-1)bar(-1). Key catalyst precursors have been characterized by X-ray crystallography.

Journal Article↗
PubMed2005

Polyethylene chain growth on zinc catalyzed by olefin polymerization catalysts: a comparative investigation of highly active catalyst systems across the transition series.

Highly active transition metal ethylene polymerization catalysts across the transition series have been investigated for their ability to catalyze chain growth on zinc. In reactions of various catalysts with ZnEt(2), product distributions range from Schulz-Flory to Poisson, with several catalysts showing intermediate behavior. A statistical modeling program is introduced to correlate product distributions with the relative rates of propagation, chain transfer to zinc, and beta-H transfer. Six regimes have been identified, ranging from Schulz-Flory to pure Poisson where chain transfer to metal is the only termination process, through to combined alkane/alkene distributions where beta-H transfer is competitive with chain transfer to metal. It is concluded that, while catalyzed chain growth (CCG) is favored by a reasonable match between the bond dissociation energies of both the main group and transition metal alkyl species, the M-C bond energies of the bridging alkyl species, and hence the stabilities of any hetero-bimetallic intermediates or transition states, are key. The latter are strongly influenced by the steric environment around the participating metal centers, more bulky ligands leading to a weakening of the bonds to the bridging alkyl groups; CCG is thus usually more favored for sterically hindered catalysts.

Journal Article↗
PubMed2005

Pyridine N-alkylation by lithium, magnesium, and zinc alkyl reagents: synthetic, structural, and mechanistic studies on the bis(imino)pyridine system.

The 2,6-bis(alpha-iminoalkyl)pyridines 2,6-[ArNC(CR(3))](2)C(5)H(3)N [R = H, D; Ar = 2,6-i-Pr(2)C(6)H(3) (DIPP), 2,6-Me(2)C(6)H(3) (DMP)] react with MeLi in Et(2)O to give a binary mixture of products: the pyridine N-methylated species 2,6-[ArNC(CR(3))](2)C(5)H(3)N(Me)Li(OEt(2)) and the deprotonated/dedeuterated species 2-[ArNC(CR(3))],6-[ArNC(=CR(2))]C(5)H(3)NLi(OEt(2)). For R = D, the product ratio is 2:1 in favor of the N-methylated product, while, for R = H, the deprotonated product is favored by 5:1, increasing to 8:1 in toluene solvent. Warming solutions of the N-methylated species leads to clean conversion to the thermodynamically preferred deprotonated species. Crossover experiments show that MeLi is re-formed and dissociates from the terdentate ligand before deprotonating the ketimine methyl unit. For MgR(2) (R = Et, i-Pr) and ZnR(2) (R = Et) reagents, N-alkylation products are formed exclusively, but derivatives containing bulky aryl substituents are found to undergo further rearrangement to 2-alkylated species, arising by migration of the alkyl group of the N-alkyl moiety to the adjacent ring carbon atom. The reversibility of the N-alkylation process has been probed using deuterio-labeled Mg alkyl reagents and mixed alkyl zinc species. A cationic zinc derivative is shown to undergo "reverse" alkyl migration, from the heterocycle nitrogen atom to the zinc center. EPR spectroscopy reveals a paramagnetic intermediate in which the unpaired electron is delocalized over the heterocycle and di-imine moieties of the ligand, indicating that the N-alkylation reactions proceed via single electron-transfer processes.

Journal Article↗
PubMed2005

A computational analysis of the ring-opening polymerization of rac-lactide initiated by single-site beta-diketiminate metal complexes: defining the mechanistic pathway and the origin of stereocontrol.

The ring-opening polymerization of rac-lactide at a beta-diketiminate magnesium center, [HC{CMeN-2,6-(i)Pr(2)C(6)H(3)}(2)]Mg(OMe)(THF), has been investigated using a B3-LYP density functional procedure employing three different layers of basis set: 6-311G(3d) at the Mg center, 6-31G(d) for both the ligand skeleton and the monomer, and a STO-3G basis set at the bulky 2,6-diisopropylphenyl substituents. By studying the consecutive ring-opening of two lactide molecules, clear conclusions are drawn regarding both the mechanism of ring-opening and the origin of heterotactic stereocontrol observed with such initiators. Polymerization proceeds via two major transition states, an observation applicable to other coordinative initiator systems, with the highest energy transition state dictating the stereochemistry of monomer insertion. In the beta-diketiminate magnesium system, a detailed examination of the rate-limiting second transition state geometries reveals that heterotactic poly(lactic acid) arises via the minimization of several steric interactions, possibly reinforced by an attractive CH...pi interaction.

Journal Article↗