2,6‐(Diphenylmethyl)‐4‐alkyl‐phenyl substituted phosphates, ArOP(O)(OH)2 (Ar=2,6‐CHPh2‐4‐R‐C6H2; R=Me (9), Et (10), iPr (11), and tBu (12)), were synthesized from the corresponding phenols. The single crystals of these compounds were obtained from their solutions of CH3CN or CH3COCH3. The molecular structures of these compounds, in the solid state, determined by single crystal X‐ray analysis reveal that they possess a hitherto unknown structural motif among monoorganophosphate esters viz., a dimeric hydrogen bonded structure involving a P−OH donor and a P=O acceptor group affording an eight‐membered ring. This structural motif is similar to what is commonly found in the solid state structures of carboxylic acids. In all of these compounds the solid state structure is restricted to the dimeric motif except in 9 where a 1D hydrogen‐bonded polymer formation is observed when it crystallized from acetonitrile. Deprotonation of these monoorganophosphates with triethylamine afforded the anionic phosphates, [ArOP(O)(OH)(O)]− containing Et3NH+ as the counter cation (Ar=2,6‐CHPh2‐4‐R‐C6H2; R=Me (13), Et (14), iPr (15), and tBu (16)). The solid state molecular structures of 13–16 again reveal hydrogen‐bonded dimeric structures in the solid state. In order to demonstrate the proof‐of‐principle with regard to the reactivity of the monoorganophosphates, we explored the reaction of 9 with ZnCl2 in the presence of pyrazole (PzH) and Et3N affording a dinuclear Zn(II) complex, [Et3NH]2[{ArOP(O)3}2{Zn(Cl)(PzH)}2] (Ar=2,6‐CHPh2‐4‐Me–C6H2) (17). The two Zn(II) centers are linked to each other by two dianionic [ArOP(O)3]2− ligands. Two additional triethylammonium cations and a terminal Zn−Cl moiety compensate the charge and complete the composition of 17.

Herein, the isolation and characterization of N-peralkyl-substituted NHC-CAAC derived triazaalkenes in three oxidation states, neutral, radical cation, and dication, are reported. Cyclic voltammetry has shown the reversible electronic coupling between the first and second oxidation to be ΔE = 0.50 V. As a proof-of-principle, to demonstrate the electron-rich nature of the triazaalkene, it was shown that it can be used as an electron donor in the reduction of an aryldiazonium salt to the corresponding arene.

We report the synthesis and isolation of molecular iron germanide motifs in the stoichiometry of Fe Ge and Fe Ge, which are stabilized by the coordination of N-heterocyclic carbene (NHC) and carbon monoxide (CO) ligands. NHCiPr2Me2 ⋅Ge[Fe(CO) ][Fe (CO) ] (NHCiPr2Me2 =1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene), a germanium(0) ligand with just one NHC as an auxiliary ligand, assumes a bridging coordination mode between a mononuclear [Fe(CO) ] and a dinuclear [(CO) FeFe(CO) ] unit with rapid exchange between the two binding modes in solution. The electronic structure of this species is analysed by NBO and ELF calculations with DFT methods, as well as the mechanistic details of its fluxional coordination behaviour. Treatment of NHCiPr2Me2 ⋅Ge[Fe(CO) ] [Fe (CO) ] with the sterically less demanding NHCMe4 (NHCMe4 =1,3,4,5-tetramethylimidazol-2-ylidene) leads to a dinuclear iron complex (NHCMe4 ) Ge[Fe(CO) ] that contains a bridging germylone ligand with two stabilizing NHC equivalents.

NHC-stabilized 2-hydrophosphasilenes are obtained from 1,2-dihydro-2-chlorophosphasilanes as Si(iv) precursors by a NHC-assisted 1,2-elimination of HCl. The NHC-exchange of these compounds is demonstrated as a proof of donor acceptor bonding between NHC and the silicon centre of the "Si[double bond, length as m-dash]P" moiety. We have also explored the possibility of similar exchanges in NHC-stabilized Si and P compounds. Theoretical DFT calculations were performed to address the nature of Si-P bonding in the NHC-stabilized 2-hydrophosphasilenes.