Tethered Alkylidenes for REMP from Carbon Disulfide Cleavage.

Reactions between tungsten alkylidyne [BuOCO]W≡CBu(THF) and sulfur containing small molecules are reported. Complex reacts with CS to produce intermediate η bound CS complex [OC(BuC═)W(η-(,)-CS)(THF)] . Heating complex provides a mixture of a monomeric tungsten sulfido complex and a dimeric complex in a 4:1 ratio, respectively.

Probing borafluorene B-C bond insertion with gold acetylide and azide.

The reaction of PhPAuN with 9-Ph-9-borafluorene resulted in complexation of the azide to boron while a gold acetylide reacted with 9-Ph-9-borafluorene to insert the acetylide carbon to access a six-membered boracycle with an exocyclic double bond.

iClick synthesis of network metallopolymers.

Described is an approach to preparing the first iClick network metallopolymers with porous properties. Treating digoldazido complex 2-AuN3 with trigoldacetylide 3-AuPPh3 or 3-AuPEt3, trialkyne 3-H, tetragoldacetylide 4-AuPPh3, or tetraalkyne 4-H in CHCl affords five iClick network metallopolymers 5-AuPPh3, 5-AuPEt3, 5-H, 6-AuPPh3, and 6-H. Confirmation of the iClick network metallopolymers comes from FTIR, C solid-state cross-coupling magic angle spinning (CPMAS) NMR spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and nitrogen and CO sorption analysis.

SPAAC iClick: progress towards a bioorthogonal reaction in-corporating metal ions.

Combining strain-promoted azide-alkyne cycloaddition (SPAAC) and inorganic click (iClick) reactivity provides access to metal 1,2,3-triazolates. Experimental and computational insights demonstrate that iClick reactivity of the tested metal azides (LM-N, M = Au, W, Re, Ru and Pt) depends on the accessibility of the azide functionality rather than electronic effects imparted by the metal. SPAAC iClick reactivity with cyclooctyne is observed when the azide functionality is sterically unencumbered, [Au(N)(PPh)] (Au-N3), [W(η-allyl)(N)(bpy)(CO)] (W-N3), and [Re(N)(bpy)(CO)] [bpy = 2,2'-bipyridine] (Re-N3).

Excited-State Turn-On of Aurophilicity and Tunability of Relativistic Effects in a Series of Digold Triazolates Synthesized via iClick.

iClick reactions between Au(I) acetylides PPhAu-C≡CR, where R = nitrophenyl (PhNO), phenyl (Ph), thiophene (Th), bithiophene (biTh), and dimethyl aniline (PhNMe), and Au(I)-azide PPhAuN provide digold complexes of the general formula -1,5-bis-triphenylphosphinegold(I) 1,2,3-triazolate (). Within the digold triazolate complexes the Au(I) atoms are held in close proximity but beyond the distance typically observed for aurophilic bonding. Though no bond exists in the ground state, time-dependent density functional theory interrogation of the complexes reveals excited states with significant aurophilic bonding.

Mass spectrometry-based identification of carbohydrate anomeric configuration to determine the mechanism of glycoside hydrolases.

A rapid mass spectrometry method for determining the anomeric configuration of the sugar at the reducing end of an oligosaccharide was demonstrated. The method was employed to identify the nascent anomeric configuration (i.e.

Reduced thione ligation is preferred over neutral phosphine ligation in diiron biomimics regarding electronic functionality: a spectroscopic and computational investigation.

Sulfur containing ligands with a thiolate-thiyl radical character are much superior than phosphine ligands in the active site modeling of [FeFe]hydrogenase regarding electronic functionality on charge communication and modulation of the electronic structure of the catalytic metal center.