The dinuclear complex Cp*2Os2Br4 (Cp* ) pentamethylcyclopentadienyl) and related mono(pentamethylcyclopentadienyl)osmium compounds are catalysts for the ring-opening metathesis polymerization (ROMP) of norbornene. The most active catalyst prepared to date is made by treatment of Cp*2Os2Br4 with methylaluminoxane. This catalyst polymerizes norbornene with yields up to 167 kg of polymer per mol o...

The synthesis and electrochemical properties of novel block copolymers are reported. Three different norbornene derivatives having phenylene-thiophene, phenylene-bithiophene, and phenylene-furan structures were copolymerized with either norbornene or 7-oxanorbornene derivatives via ring-opening metathesis polymerization (ROMP). Block copolymers’ stabilities and solubilities could be improved by...

A modular system for the construction of radiometalated antibodies was developed based on the bioorthogonal cycloaddition reaction between 3-(4-benzylamino)-1,2,4,5-tetrazine and the strained dienophile norbornene. The well-characterized, HER2-specific antibody trastuzumab and the positron emitting radioisotopes (64)Cu and (89)Zr were employed as a model system. The antibody was first covalentl...

We report the surface-initiated growth of poly(alkylnorbornene) films via ring-opening metathesis polymerization (ROMP). The films are grown by exposure of a vinyl-terminated self-assembled monolayer (SAM) on gold to Grubbs first-generation catalyst and the subsequent exposure to an alkylnorbornene monomer. We investigate the influence of alkyl side chains on the structure, barrier, surface pro...

The tetrathioperrhenate anion, ReS4 (1), is shown to form adducts with a variety of alkenes. The alkene adducts form reversibly, and those of norbornene and norbornadiene were isolated. For norbornene, the Keq’s range from 12 000 (CH2Cl2 solution) to 2650 M-1 (pyridine solution). The following values were determined (MeCN soln): ∆H ) -53 kJ mol-1 and ∆S ) -98 J‚mol-1‚K-1. The solid-state struct...

Antioxidant norbornene-based monomers bearing biobased sterically hindered phenols (SHP)-NDF (norbornene dihydroferulate) and NDS (norbornene dihydrosinapate)-have been successfully prepared through biocatalysis from naturally occurring ferulic and sinapic acids, respectively, in presence of Candida antarctica Lipase B (Cal-B). The ring opening metathesis polymerization (ROMP) of these monomers...

Here, we report a simple synthetic strategy to the bridgehead vicinal diallylation of norbornene derivatives. These substrates are useful to generate propellanes via ring-closing metathesis. Single-crystal X-ray diffraction analysis of four compounds led to the realization of configurational correction of earlier reported molecules.

Cycloaddition reactions involving tetrazines have proven to be powerful bioorthogonal tools for various applications. Conceivably, sequential and selective labeling using tetrazine-based reactions can be achieved by tuning the reaction rate. By varying the substituents on tetrazines, cycloaddition rate variations of over 200 fold have been achieved with the same dienophile. Upon coupling with d...

Rare earth metal bis(alkyl) complexes attached by fluorenyl modified N-heterocyclic carbene (NHC) (Flu-NHC)Ln(CH(2)SiMe(3))(2) (Flu-NHC = (C(13)H(8)CH(2)CH(2)(NCHCCHN)C(6)H(2)Me(3)-2,4,6); Ln = Sc (2a); Y (2b); Ho (2c); Lu (2d)), ((tBu)Flu-NHC)Ln(CH(2)SiMe(3))(2) ((tBu)Flu-NHC = 2,7-(t)Bu(2)C(13)H(6)CH(2)CH(2)(NCHCCHN)C(6)H(2)Me(3)-2,4,6; Ln = Sc (1a); Lu (1d)) and attached by indenyl modified ...

Palladium-catalyzed hydroarylations and additional domino reactions of aza-bicyclic and tricyclic norbornene derivatives were investigated and a series of new epibatidine analogues were synthesized.