Can carbene decorated [FeFe]-hydrogenase model complexes catalytically produce dihydrogen? An insight from theory.

Cyclic alkyl amino carbene (CAAC) anchored [FeFe]-hydrogenase model complex featuring rotated conformation at one of the iron centers are found to be promising candidate for effective production of dihydrogen. A stepwise comparison of the complete mechanism using the CAAC stabilized model complex [1]0 has been performed with that of an experimentally isolated one ([2]0). Interestingly, the reduction events involved in the catalytic cycles are found to be more favorable than those previously reported for a similar experimentally known system. Furthermore, the computed ΔpKa values indicate that the distal iron center with a vacant coordination site is more basic compared to the amino nitrogen atom of the azadithiolate bridge. We also made an attempt to determine the oxidation states of the iron centers for the intermediates involved in the catalytic cycles on the basis of the computed Mössbauer isomer shift and Mulliken spin density values.

Strategies toward realization of unsupported transition metal-boron donor-acceptor complexes: an insight from theory.

Pre-pyramidalization of the boron centre in the Lewis acidic groups is a prerequisite for the formation of unsupported donor-acceptor complexes with Lewis basic metal fragments such as [Pt(NHC)2].

Release of Isonitrile- and NHC-Stabilized Borylenes from Group†VI Terminal Borylene Complexes.

A family of doubly isonitrile-stabilized terphenyl borylenes could be obtained by addition of three equivalents of isonitrile to the corresponding Cr and W terminal terphenyl-borylene complexes. The mechanism of isonitrile- and carbon-monoxide-induced borylene liberation was investigated computationally and found to be significantly exergonic in both cases. Furthermore, addition of a small N-heterocyclic carbene (NHC) to a terminal Cr borylene complex results in release of an NHC-stabilized borylene carbonyl species, whereas the analogous reaction with bulkier phosphines results in metal-centered substitution.

Synthesis and Trapping of Iminoboranes by M=B/C=N Bond Metathesis.

Although the metathesis of metal-boron double bonds with elemental chalcogenides is an established process, no similar reactivity has been observed with element-nitrogen bonds. Such a reaction would provide a new route to iminoborane compounds (RB≡NR'), which have recently experienced renewed synthetic interest. Herein, we present the first observation of M=B/C=N metathesis reactions, which led to the isolation of a stable iminoborane in addition to further iminoborane cycloaddition products.

Theoretical strategies toward stabilization of singlet remote N-heterocyclic carbenes.

Theoretical investigations predict that the singlet states of ylide-substituted remote carbenes are significantly stable and comparable to those of experimentally known NHCs. They are also found to be strongly σ-donating in nature as evident from an evaluation of the carbonyl stretching frequencies (νCO ) of their complexes with the [Rh(CO)2 Cl] fragment. NICS and QTAIM based bond magnetizability calculations indicate the presence of cyclic electron delocalization in majority of the molecules. © 2016 Wiley Periodicals, Inc.

Annulated boron substituted N-heterocyclic carbenes: theoretical prediction of highly electrophilic carbenes.

Theoretical calculations were carried out to understand the effect of annulation on the electronic and ligand properties of boron substituted N-heterocyclic carbenes (B-NHCs). Annulation results in a decrease in stability as indicated by the calculated values of singlet-triplet separations and stabilization energies as well as HOMO-LUMO gaps. Annulated B-NHCs are found to be weaker σ-donors but better π-acceptors than the parent ones. The decrease in σ-donation ability and the increase in π-accepting ability are further supported by the calculated values of proton affinities, nucleophilicity and electrophilicity indices as well as (31)P NMR chemical shifts of the corresponding NHC-PPh adducts. Most of the annulated B-NHCs are found to have significantly enhanced electrophilicity than the other known carbenes.

Moving toward Ylide-Stabilized Carbenes.

The effect of ylide substitution at the α position to the carbene carbon (Cc ) atom on the stability and σ-donating ability of a number of cyclic carbenes has been studied theoretically. The stabilities of all of the carbenes were investigated from an evaluation of their singlet-triplet energy gaps and stabilization energies. All carbenes were found to have a stable singlet state. The energy of the σ-symmetric lone-pair orbital at the Cc atom increases as a result of the introduction of ylide centers near to the Cc atom. This indicates an enhanced σ-donating ability of the ylide-containing carbenes. The calculated carbonyl-stretching frequencies of the corresponding rhodium complexes, proton affinities, and nucleophilicity index values correlate well with the σ basicity of the carbenes.

Spectroscopic Distinction of Different Carbon Bases: An Insight from Theory.

Spectroscopic differentiation based on the (13)C NMR chemical shift of the parent and protonated derivatives of carbon(II) and carbon(0) bases has been proposed. The (13)C chemical shift of the central carbon atom of carbenes in their parent and protonated forms will experience more downfield shift, whereas the central carbon atom of carbones will experience a lesser downfield shift; such shifts for compounds that possess "hidden" carbon(0) characteristics will lie between these two extremes. The (13)C chemical shifts of the protonated derivatives are solely dependent on the out-of-plane pπ occupancies of the central carbon atom. This difference arises due to their unique difference in bonding and may provide an easier distinction between these two classes of compounds.

Tuning the electronic and ligand properties of remote carbenes: a theoretical study.

The effect of annulation and carbonylation on the electronic and ligating properties of remote N-heterocyclic carbenes (rNHCs) has been studied quantum-chemically. The thermodynamic stability of these complexes has been assessed on the basis of their hydrogenation and stabilization energies, while HOMO-LUMO gaps are used to measure the kinetic stabilities. Annulated/carbonylated rNHCs are found to be weaker σ donors but better π acceptors compared with the parent rNHCs. The reactivity of these rNHCs has been studied by evaluating their nucleophilicity and electrophilicity indices. The nucleophilicity values are in good agreement with the σ basicities of all of the rNHCs. The (31)P NMR chemical shifts of the corresponding rNHC-phosphinidene adducts have been calculated and found to correlate well with the π acidities of these rNHCs.