Ring opening polymerization of lactides and lactones by multimetallic alkyl zinc complexes derived from the acids Ph₂C(X)CO₂2H (X = OH, NH₂ )

The reaction of the dialkylzinc reagents R₂Zn with the acids 2,2-Ph₂C(X)(CO₂H), where X = NH₂, OH, i.e. 2,2′-diphenylglycine (dpgH) or benzilic acid (benzH2), in toluene at reflux temperature afforded the tetra-nuclear ring complexes [RZn(dpg)]₄, where R = Me (1), Et (2), 2-CF₃C₆H₄ (3), and 2,4,6-F₃C₆H₂ (4); complex 2 has been previously reported. The crystal structures of 1·(2MeCN), 3 and 4·(4(C₇H₈)·1.59(H₂O)) are reported, along with that of the intermediate compound (2-CF₃C₆H₄)3B·MeCN and the known compound [ZnCl₂(NCMe)₂]. Complexes 1–4, together with the known complex [(ZnEt)₃(ZnL)₃(benz)₃] (5; L = MeCN), have been screened, in the absence of benzyl alcohol, for their potential to act as catalysts for the ring opening polymerization (ROP) of ε-caprolactone (ε-CL), δ-valerolactone (δ-VL) and rac-lactide (rac-LA); the co-polymerization of ε-CL with rac-LA was also studied. Complexes 3 and 4 bearing fluorinated aryls at zinc were found to afford the highest activities

Mixed-magnesium/zinc calix[4]arene complexes: Structure, and ring opening polymerisation studies

Different combinations of organomagnesium reagents and zinc bromide react with either 1,3-dimethoxy-4-tert-butylcalix[4]areneH2 (L(OMe)2H2) or trialkoxycalix[4]arenes (L(OR)3H) (R = n-Pr, n-pentyl) to afford mixed-metal calix[4]arene systems. Intruiging molecular structures are formed and the systems are capable of the ring opening polymerisation of ε-caprolactone under N2, air, or as melts

5,7-Dihy­droxy-3,6-dimeth­oxy-2-(4-meth­oxy­phen­yl)-4H-chromen-4-one monohydrate

The title compound, C18H16O7·H2O, is a flavonoid isolated from Dodonaea viscosa­. The benzopyran ring system of the flavonoid is essentially planar [maximum deviation = 0.025 (2) Å] and inclined at 5.83 (2)° to the attached benzene ring. The water of hydration is involved in extensive hydrogen bonding, assembling the mol­ecules into a supra­molecular network via classical inter­molecular O—H⋯O hydrogen bonding. The crystal structure is further stabilized by π–π stacking inter­actions [centroid–centroid distance between benzene rings = 3.564 (3) Å]

Reaction of Ph2C(X)(CO2H) (X = OH, NH2) with [VO(OR)3] (R = Et, nPr): Structure, magnetic susceptibility and ROP capability

Reaction of [VO(OR)3] (R = Et, nPr) with 2,2′-diphenylglycine afforded the alkoxide-bridged dimers {[VO(OR)(μ-OR)][Ph2C(NH2)(CO2)]}2, whereas use of benzilic acid, in the presence of alkali metals, afforded 16-membered metallocycles {V8(O)4M(OR)8[Ph2C(OH)(CO2)]12} (M = <1 Na, K). For the ring systems, magnetic susceptibility data is consistent with mixed-valence vanadium with an average oxidation state of 3.5. The dimer and ring systems are capable of the ring opening polymerisation (ROP) of ϵ-caprolactone under N2, air, or as melts affording mostly low to medium molecular weight cyclic and linear products

The selective mono and difunctionalization of carbocyclic cleft molecules with pyridyl groups and X-ray crystallographic analysis

The diesterification and selective mono and dialkylation of carbocyclic analogues of Tröger’s base with pyridyl groups has been achieved in high yield and good selectivity giving access to a novel range of cleft molecules capable of binding events. Reaction conditions for the selective functionalization of this carbocyclic cleft molecule are discussed as well as the solid state structures of these newly synthesized ligands

Vanadyl sulfates: molecular structure, magnetism and electrochemical activity

Reaction of differing amounts of vanadyl sulfate with p-tert-butylthiacalix[4]areneH4 and base allows access to the vanadyl-sulfate species [NEt4]4[(VO)4(μ3-OH)4(SO4)4]·½H2O (1), [HNEt3]5[(VO)5(μ3-O)4(SO4)4]·4MeCN (2·4MeCN) and [NEt4]2[(VO)6(O)2(SO4)4(OMe)(OH2)]·MeCN (3·MeCN). Similar use of p-tert-butylsulfonylcalix[4]areneH4, p-tert-butylcalix[8]areneH8 or p-tert-butylhexahomotrioxacalix[3]areneH3 led to the isolation of [HNEt3]2[H2NEt2]2{[VO(OMe)]2p-tert-butylcalix[8-SO2]areneH2} (4), [HNEt3]2[V(O)2p-tert-butylcalix[8]areneH5] (5) and [HNEt3]2[VIV2VV4O11(OMe)8] (6), respectively. Dc magnetic susceptibility measurements were performed on powdered microcrystalline samples of 1–3 in the T = 300–2 K temperature range. Preliminary screening for electrochemical water oxidation revealed some activity for 2 with turnover frequency (TOF) and number (TON) of 2.2 × 10−4 s−1 and 6.44 × 10−6 (mmol O2/mmol cat.), respectively. The compound 3 showed an improved electrochemical activity in the presence of water. This is related to the increased number and the rate of electrons exchanged during oxidation of V4+ species, facilitated by protons generated in the water discharge process

The selective mono and difunctionalization of carbocyclic cleft molecules with pyridyl groups and X-ray crystallographic analysis

This article was published in the journal Tetrahedron [© Elsevier Ltd]. The definitive version is available at: http://dx.doi.org/10.1016/j.tet.2010.10.027The diesterification and selective mono and dialkylation of carbocyclic analogues of Tröger’s base with pyridyl groups has been achieved in high yield and good selectivity giving access to a novel range of cleft molecules capable of binding events. Reaction conditions for the selective functionalization of this carbocyclic cleft molecule are discussed as well as the solid state structures of these newly synthesized ligands

Vanadyl sulfates:molecular structure, magnetism and electrochemical activity

Reaction of differing amounts of vanadyl sulfate with p-tert-butylthiacalix[4]areneH4 and base allows access to the vanadyl-sulfate species [NEt4]4[(VO)4(3-OH)4(SO4)4]∙1/2H2O (1), [HNEt3]5[(VO)5(3-O)4(SO4)4]∙4MeCN (2∙4MeCN) and [NEt4]2[(VO)6(O)2(SO4)4(OMe)(OH2)]∙MeCN (3∙MeCN). Similar use of p-tert-butylsulfonylcalix[4]areneH4, p-tert-butylcalix[8]areneH8 or p-tert-butylhexahomotrioxacalix[3]areneH3 led to the isolation of [HNEt3]2[H2NEt2]2[VO(OMe)]2p-tert-butylcalix[8-SO2]areneH2] (4), [HNEt3]2[V(O)2p-tert-butylcalix[8]areneH5] (5) and [HNEt3]2[VIV2VV4O11(OMe)8] (6), respectively. Dc magnetic susceptibility measurements were performed on powdered microcrystalline samples of 1-3 in the T = 300 - 2 K temperature range. Preliminary screening for electrochemical water oxidation revealed some activity for 2 with turnover frequency (TOF) and number (TON) of 2.2 × 10-4 s-1 and 6.44 × 10-6 (mmol O2 / mmol cat.), respectively. The compound 3 showed an improved electrochemical activity in the presence of water. This is related to the increased number and the rate of electrons exchanged during oxidation of V4+ species, facilitated by protons generated in the water discharge process

Cellular uptake studies of two hexanuclear, carboxylate bridged, zinc ring structures using fluorescence microscopy

Two hexanuclear zinc complexes have been structurally characterized, and evaluation against several cells showed selective toxicity. Cellular uptake revealed a non-specific process, resulting in accumulation within the cell cytoplasm. © 2012 The Royal Society of Chemistry

Mixed-magnesium/zinc calix[4]arene complexes: structure, and ring opening polymerisation studies

Different combinations of organomagnesium reagents and zinc bromide react with either 1,3-dimethoxy-4-tert-butylcalix[4]areneH2 (L(OMe)2H2) or trialkoxycalix[4]arenes (L(OR)3H) (R = n-Pr, n-pentyl) to afford mixed-metal calix[4]arene systems. Intruiging molecular structures are formed and the systems are capable of the ring opening polymerisation of ε-caprolactone under N2, air, or as melts.</p