Anti-Bu-1A monoclonal antibody, clone BW30 [Biotin]

Reaction of [Cp*Ti((NN)-N-Xyl){N-NPh2)(NH2'Bu)] (1a) with 1 molar equiv of phenylallene resulted in the formation of a mixture of the two metallacyclic compounds [Cp*Ti((NN)-N-Xyl){kappa N-2(NPh2)-(C(CHPh)CH2}] (2a and 2b) in a molar ratio of 3:1. Comparison of the C-13 and N-15 NMR resonances with the computed chemical shifts, along with an X-ray diffraction study of 2a, allowed the assignment of the diastereomers as the cycloadducts derived from a (3,2)-cycloaddition of the allene to the Ti=N bond. Upon reaction of I a with phenylisothiocyanate, two complexes were formed in a 3:1 ratio. The major isomer, [Cp*Ti((NN)-N-Xyl){kappa(2)-N(NPh2)C(NPh)S}] (4a), was isolated and identified by X-ray diffraction to result from a [2+2] cycloaddition of the C=S bond in PhNCS to the Ti=N bond of the hydrazinediido unit, giving a four-membered metallacyclic ring with an S,N-coordination to the titanium center and an exocyclic C=N double bond. In the minor compound (4b) the two nitrogen atoms of the thiourea unit formed in the cycloaddition are coordinated to the titanium center. Isomerization between the cycloadducts occurs only in the direction 4b - 4a, and crossover experiments indicate a dissociative mechanism (via a retro-cycloaddition) for the rearrangement. The reaction of 1a with PhNCO gave analogous N,O- and N,N-coordinated cycloadducts. Finally, the N,N-dimethyl hydrazinediido complexes reacted unspecifically with most organic azides at ambient temperature. However, complex [Cp*Ti((NN)-N-Xyl){N-NMe2}(dmap)] (1c) underwent a clean and fast reaction with trimethylsilylazide to give the N-silylated eta(2)-hydrazido(1-) titanium azide [Cp*Ti-((NN)-N-Xyl)(eta(2)-NMe-NSiMe3)(N-3)] (8), in which the trimethylsilyl group of the azide is transferred to the hydrazido ligand, while the azide is terminally coordinated to the titanium center.

Diphenylacetylenes having various silyl groups (PhC equivalent to CC6H4-(SiRRR3)-R-1-R-2, (SiRRR3)-R-1-R-2 = p-SiMe3, p-SiMe(2)i-Pr, p-SiEt3, p-SiMe(2)n-C8H17, p-SiMe(2)n-C18H37, m-SiMe3, m-SiMe(2)t-Bu, 1a-g, respectively) were polymerized with TaCl5-n-Bu4Sn catalyst to provide high molecular weight polymers. The formed polymers (2a-g) afforded tough free-standing membranes by casting from toluene solution. Desilylation of these Si-containing polymer membranes was carried out with trifluoroacetic acid. Para-substituted polymers (2a-e) underwent desilylation completely, while meta-subustituted polymers (2f and 2g) did not. According to thermogravimetric analysis (TGA), both Si-containing and desilylated polymers exhibited high thermal stability, and all the desilylated polymers showed practically the same onset temperature (similar to 480 degrees C) of weight loss. The membranes of Si-containing polymers showed lower oxygen permeability as the silyl group became bulkier. The oxygen permeability coefficients (P(O-2) 120-3300 barrers) of desilylated polymer membranes were quite different from each other irrespective of the same polymer structure. When bulkier silyl groups were removed, the oxygen permeability increased to larger extents. In ethanol/water pervaporation, both Si-containing and desilylated polymer membranes showed ethanol permselectivity, indicating that these membranes possess large excess free volumes.