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Cyclic voltammetry was employed to investigate the electrochemical behavior of numerous cyclopentadienyliron (CpFe+) and pentamethyl-cyclopentadienylruthenium (Cp*Ru+) coordinated oligomers and polymers. The electrochemical behavior of the iron systems indicated the cyclopentadienyliron complexes ha...
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A variety of homometallic (Cp*Ru+) and heterometallic (CpFe+–Cp*Ru+) oligomers with one to five metal moieties were prepared in high yields (74–90%) via nucleophilic aromatic substitution reactions. For the mixed metal systems, it is shown that the arrangement of the metal moieties along the bac...
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The through space singlet-singlet and triplet-triplet energy transfers in cofacial bis(etio-porphyrins) rigidly held by the carbazoyl spacer were investigated. The studies on singlet-singlet transfer, which operates via a Förster mechanism, were performed using the zinc porphyrin and free base chro...
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Three conjugated polymers of the type (-spacer-CtC-PtL2-CtC-)n, with spacer ) para- and orthobis( diphenyl(tetramethoxy)quinone diimine) and L ) PEt3, were synthesized as the cis- and trans-isomers about the Pt. The three combinations (spacer/PtL2Cl2), ortho/trans, para/trans, and para/cis led to po...
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A review. The unique features of dendritic architecture and the rich chem. of organo-transition metal complexes were combined in metallodendrimers to create the potential for a wide range of utilitarian applications. Because dendrimers allow scientists to probe the twilight zone between homogeneous ...
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Pyrazole derivs. are well documented to possess anti-inflammatory activity but their effects on microglial activation are unknown. We detd. the efficacy of the novel pyrazole compd. 2-MBAPA (R/S-(±)-2-Methylbenzylamino 2-oxo-N-[4-cyano-1-phenyl-1H-pyrazol-5-yl] acetamide) on activated microglia u...
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In this investigation, the hydration characteristics and microstructure of calcium aluminate cement (CAC) contg. different proportions of high slag (HSC) and sulfate resisting cements (SRC) were studied. The blends were made from CAC with the partial replacement of HSC or SRC of 5, 10, 15, 20 and 25...
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The ring-opening metathesis copolymerizations of deltacyclene, substituted deltacyclene, and norbornene was achieved using RuCl3, ReCl5, and molybdenum alkylidene catalysts. The reaction conditions employed are similar to those used previously in the syntheses of homopolymers. The low conversion cop...
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A range of oxabicyclo[3.2.l]octenes has been found to undergo opening when treated with organolithium reagents. Up to five stereocenters are created in two steps. Oxidative cleavage leads to a stereocontrolled synthesis of polysubstituted cycloheptanediols.
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Ring-opening metathesis polymn. of the title monomer (I) occurred in the presence of RuCl3 to give high-mol.-wt. unsatd. polymers contg. highly strained and reactive cyclopropane rings. The effects of water, solvent, catalyst-I ratio, and temp. on polymer wt.-av. mol. wt. were detd. A mixt. of cis a...
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The Vyazovkin model-free method were applied to study non-isothermal degrdn. of an aryl and hetaryl azo dye-contg. polynorbornene using a differential scanning calorimetric (DSC) technique. The samples were heated in nitrogen, with heating rates in the range 5-50 K min-1. The isoconversional method ...
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The kinetics involved in the thermal degradation of an aryl azo dye-containing polynorbornene was investigated by using isothermal DSC data. The activation energy of the degradation was found to be temperature dependent with two different values of 140 ± 5 and 21 ± 2 kJ mol−1, and the Avrami exp...
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Treatment of CuI with the flexible PhS(CH(2))(4)SPh dithioether ligand in MeCN solution affords the strongly luminescent metal-organic 2D coordination polymer [Cu(4)I(4){mu-PhS(CH(2))(4)SPh}(2)](n) (). The interpenetrated 2D network of is built upon by Cu(4)(mu(3)-I)(4) cubane-like clusters as secon...
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Reaction of the cyclopentadienyliron (CpFe) complex e.g. I-III with an excess of BuNH2 gave only monosubstitution of one of the two chlorogroups, whereas a similar reaction carried out in the presence of some added HOAc resulted in disubstitution of both chloro groups. However, in the reaction of I-...
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The ring-opening reaction of 7-oxabicyclo[2.2.1]hept-5-enes with cuprates is described. SN2′ attack with retention of configuration is the predominant pathway. The ring opening reaction of symmetrical and unsymmetrical 7-oxabicyclo[2.2.1]heptenes using cuprates is described. High yields of cycloh...
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The living ring-opening metathesis polymns. of deltacyclene (I) and 5-(tert-butyldimethylsiloxy)deltacyclene (II) in presence of the Schrock catalyst Mo(=CHCMe2Ph)[=N-2,6-(iso-Pr)2Ph](O-tert-Bu)2 were described. II was prepd. by first epoxidizing I, then treating this epoxide with a Lewis acid in pr...
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Reaction of [(η6-o-Cl2C6H4)Fe(η5-C5H5)][PF6] (I) with an excess of PhOH or p-MeC6H4SH in the presence of K2CO3 gave disubstitution of both chloro groups of I, whereas a similar reaction with one equiv of the nucleophile under conditions of high diln. gave monosubstitution of one of the chloro ...
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Polydeltacylene (I) having >95% cis-configuration was prepd. by ring-opening metathesis polymn. in presence of ReCl5. Treatment of I with dimethyldioxirane gave quant. epoxidn., and polynorbornene exhibited similar behavior.
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n6-Chloroarene or nitroarene-n5-cyclopentadienyliron hexafluorophosphates react readily with CF3CH2OH/K2CO3 or with piperidine or piperazine to give nucleophilic aromatic substitutions with Cl or NO2 as the leaving group, further demonstrating an activation for SNAr reactions by complexation to the ...
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A discussion of recent developments into the preparative and structural aspects of Fc-peptide conjugates is presented. In particular, the use of disubstituted Fc systems to control the structure is highlighted. The recent efforts of incorporating Fc into peptide-like oligo- and polyamides and dendri...
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Dimethylplatinum(II) complexes [PtMe2(NN)] {NN = bpy (2,2'-bipyridine), phen (1,10-phenanthroline) or bu2bpy (4,4'-di-tert-butyl-2,2'-bipyridine)} were reacted with alkyl halides (RX = EtI or EtBr, NN = bu2bpy; RX = nBuBr, NN = bpy; RX = CHPh2Br, NN = bpy, phen, or bu2bpy) to yield the Pt(IV) comple...
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A review. This chapter reviews research published on conjugated metal-contg. polymers from late 1998 to mid-2005. It includes polymers where the metal is incorporated into the backbone or the side chain of a conjugated polymer. Kingsborough and Swager wrote an excellent review of the field up to lat...