The addition of 4-trifluoromethyl-1-ethynylbenzene, phenylacetylene, or 4-ethynylanisole to P-mesityldiphenylmethylenephosphine, 1, produced photoluminescent 1,2-dihydrophosphinines 4a-c, respectively, in quantitative yield via a [4 + 2] cycloaddition. Limited reactivity was observed between 1 and non-aromatic alkynes. P-[Bis(trimethylsilyl)amino][(trimethylsilyl)methylene]phosphine, 2, and P-m...

A series of Schiff base ligands were synthesized from (1R)-camphor. Under the optimal conditions, (+)-SBAIB-a, 10 was found to be an excellent catalyst for the enantioselective addition of phenylacetylene to various aldehydes without utilizing either achiral additives or Ti(O(i)Pr)(4). This approach yielded (R)-propargylic alcohols in extremely high yields (up to 99%) and excellent enantioselec...

A simple synthetic pathway to the unknown 1,3,4-thiadiphospholes 3 and 1,3,4selenadiphospholes 4 has been developed involving reactions of the azaphosphavanada(V)cyclobutenes 2, generated in situ from the imidovanadium(V) complex tBuN = VCl3 and the phosphaalkynes 1a – d, with an excess of elemental sulfur or grey selenium, respectively. The reactions of the phosphaalkynes 1a,b with TaOCl3 or V...

The five-coordinate carbene complexes [Ru{κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}Cl(═CHR)] (2, R = Ph; 3, R = SiMe3), analogues of the Grubbs catalyst, were prepared from the dimer [Ru(μ-Cl){κP,P,Si-Si(Me)(C6H4-2-PiPr2)2}]2 (1) and the corresponding diazoalkane N2CHR. The particular structural features that result from the presence of a strongly trans directing silyl group at the pincer ligand of these ...

A novel class of stereocomplexes is described by the interaction of helically complementary poly(phenylacetylene)s (PPAs) carrying an α-methoxy-α-trifluoromethylphenylacetamide pendant group. The formation of the stereocomplex requires the presence of cis amide bonds on the external crest of the polymer to provide efficient cooperative supramolecular hydrogen bonding between matching enantiomer...

The use of the bulky hydrotris(3-mesitylpyrazolyl)borate anionic ligand has allowed the synthesis of stable Tp(Ms)Cu(alkyne) complexes (alkyne = 1-hexyne, 1, phenylacetylene, 2, and ethyl propiolate, 3). The spectroscopic and structural features of these compounds and their relative reactivity have been examined, indicating the existence of a low π back-bonding from the copper(I) centre to the ...

Covering hydrophobic regions with stabilization agents to solubilize purified transmembrane proteins is crucial for their application in aqueous media. The small molecule 2-methyl-2,4-pentanediol (MPD) was used to stabilize the transmembrane protein Ferric hydroxamate uptake protein component A (FhuA) utilized as host for the construction of a rhodium-based biohybrid catalyst. Unlike commonly u...

Significant elemental segregation is shown to exist within individual hollow silver-gold (Ag-Au) bimetallic nanoparticles obtained from the galvanic reaction between Ag particles and AuCl4(-). Three-dimensional compositional mapping using energy dispersive X-ray (EDX) tomography within the scanning transmission electron microscope (STEM) reveals that nanoparticle surface segregation inverts fro...