The first report of Z-selective macrocyclizations using a ruthenium-based metathesis catalyst is described. The selectivity for Z macrocycles is consistently high for a diverse set of substrates with a variety of functional groups and ring sizes. The same catalyst was also employed for the Z-selective ethenolysis of a mixture of E and Z macrocycles, providing the pure E isomer. Notably, an ethy...

Transition-metal complexes bearing labile ligands can be difficult to isolate and study in solution because of unwanted dinucleation or ligand substitution reactions. Metal–organic frameworks (MOFs) provide a unique matrix that allows site isolation stabilization well-defined transition-metal may importance as moieties for gas adsorption catalysis. Herein we report the development an situ anion...

A panel of acid-labile bis-norbornene cross-linkers was synthesized and evaluated for the formation of acid-degradable brush-arm star polymers (BASPs) via the brush-first ring-opening metathesis polymerization (ROMP) method. An acetal-based cross-linker was identified that, when employed in conjunction with a poly(ethylene glycol) (PEG) macromonomer, provided highly controlled BASP formation re...

We report the synthesis of Mo and W MAP complexes that contain O-2,6-(2,5-R2-pyrrolyl)2C6H3 (2,6-dipyrrolylphenoxide or ODPPR) ligands in which R = i-Pr, Ph. W(NAr)(CH-t-Bu)(Pyr)(ODPPPh) (4a; Ar = 2,6-disopropylphenyl, Pyr = pyrrolide) reacts readily with ethylene to yield a metallacyclobutane complex, W(NAr)(C3H6)(Pyr)(ODPPPh) (5). The structure of 5 in the solid state shows that it is approxi...

Products of the F+-for-O metathesis between a variety of fluorinated cations and , -unsaturated ketones have been examined using FT-ICR and sector mass spectrometry. The reactant ions CF3+, C3F7+, and CFO+ all undergo ion–molecule reactions with carbonyl compounds to replace oxygen with F+. In principle, the simple transposition of atoms corresponds to the transformation C=O → C=F+ and ought to...

Chapter 1 Reaction of W(CCMe 3)Cl 3(dme) with one equivalent of (3,5-Me 2C6H3NCH 2CH 2)3N)Li3 affords yellow, crystalline W(CCMe 3)(N3N) in good yield. The reactivity of this new alkylidyne complex towards terminal alkynes was investigated. Two other new tungsten alkylidynes, W(CCMe 3)(pyr) 3 (pyr = 2,5-dimethylpyrrolide) and W(CCMe3)(Ph 2N)3 were prepared by the addition of three equivalents o...

Two types of rod-coil block copolymers including poly(3-hexylthiophene)-block-poly(ethylene glycol) (P3HT-b-PEG) and PEG-block-polyaniline (PANI) were synthesized using Grignard metathesis polymerization, Suzuki coupling, and interfacial polymerization. Afterward, two types of single crystals were grown by self-seeding methodology to investigate the coily and rod blocks in grafted brushes and o...

ExposureofheptanesolutionsofMo(NAr)(CHCMe2Ph)(Me2Pyr)(OAr) (1a;Ar=2,6-diisopropylphenyl), Mo(NAr)(CHCMe3)(Me2Pyr)[OCMe(CF3)2] (1b), and Mo(NAr)(CHCMe2Ph)(Me2Pyr)(OSiPh3) (1c) to one atmosphere of ethylene for 12 h yields the ethylene complexes, Mo(NAr)(CH2CH2)(Me2Pyr)(OAr) (2a), Mo(NAr)(CH2CH2)(Me2Pyr)[OCMe(CF3)2] (2b), and Mo(NAr)(CH2CH2)(Me2Pyr)(OSiPh3) (2c). Addition of 1 equiv of triphenyls...