The effect and interrelationship between primary (segmental backbone) and secondary (side chain) molecular motions on thrombogenesis, independent of morphological order/disorder, crystallinity, and/or associated water is elucidated using an amorphous hydrophobic polymer of poly-[(trifluoroethoxy) (fluoroalkoxy)phosphazene] PNF. The results indicate that thrombogenesis for an amorphous hydrophob...

The activation of Ar-Si bonds in aryltrimethylsilane was investigated using a catalytic amount of t-Bu-P4 base and selective functionalizations of aryltrimethylsilanes in the absence of strong electron withdrawing groups on the aromatic rings were accomplished.

The toluene solution structure of an N-lithio(triphenyl)phosphazene (Ph(3)PNLi) mixed aggregate with lithium bromide (LiBr), 5, has been elucidated for the first time based on multinuclear magnetic resonance measurements ((1)H, (6)Li, (7)Li, (13)C and (31)P). The structure consist of two dimers [Li(mu-Z)](2) (Z= Br, NPR(3)) linked through LiX (X= N, Br) bridges. This arrangement is a cubane-lik...

An investigation into the poor activity of sulfides as catalysts for sulfonium-ylide-mediated methylene transfer to aldehydes has indicated that ylide formation is the problematic catalytic cycle step. Alkylation with traditional electrophiles does not proceed with sufficient efficiency to allow the sulfide to be used catalytically. Methyl triflate rapidly alkylates cyclic thiolanes under mild ...

High-resolution F, H, P and C solid-state NMR methods were assessed to ascertain their suitability for studying the morphological behavior in the crystalline domain of phosphazene polymers with partially fluorinated side-chains. Poly[bis(trifluoroethoxy)phosphazene] (PBFP) was used as a sample system. Fast magic angle spinning (MAS), along with simultaneous F and H decoupling using the xy-16 se...

A series of compounds of the N3P3Cl(6 - n)(NHBu(t))n family (where n = 0, 1, 2, 4 and 6) are presented, and their molecular parameters are related to trends in physical properties, which provides insight into a potential reaction mechanism for nucleophilic substitution. The crystal structures of N3P3Cl5(NHBu(t)) and N3P3Cl2(NHBu(t))4 have been determined at 120 K, and those of N3P3Cl6 and N3P3C...

Solution properties of enolates generated using the phosphazene (Schwesinger) base P4-tBu were investigated by NMR spectroscopy. With a full equivalent of base the benzyl ketones 1a and 1b, the acetophenone 2, the arylacetaldehyde 1c, and the methyl arylacetate 1d formed the expected "naked" (P4H+) enolates 3 and 7. However, at a half-equivalent of base the ketones 1a and 1b as well as the alde...