First and second proton affinities of carbon bases.

Quantum chemical calculations at the MP2/TZVPP//BP86/SVP level are reported for the first and second proton affinities (PAs) of divalent carbon-donor molecules. The molecules investigated are imidazol-2-ylidenes ("normal" NHCs) and the tautomeric imidazol-4/5-ylidenes ("abnormal" NHCs). PAs are also calculated for acyclic and cyclic carbodiphosphoranes, carbophosphoranesulfide, unsaturated and saturated carbodicarbenes, tetraaminoallenes and carbon suboxide. The results are discussed in terms of divalent carbon(II) compounds (carbenes) CR(2), which have one lone electron pair at carbon, and carbon(0) compounds CL(2), which have two lone pairs at carbon and two C<--L donor-acceptor bonds. Divalent C(0) compounds (carbones) not only have very high first PAs, but the second PA is also large and strong enough to isolate doubly protonated C(0) species as salts in a condensed phase. The first PA of divalent carbon(II) compounds (carbenes) are also large. However, they have much smaller second PAs than the divalent carbon(0) compounds. The divalent C(0) character of a compound is not always obvious when the bonding situation in the equilibrium geometry is considered. This is the case, for example, for tetraaminoallenes (TAAs). Protonation of TAAs changes the bonding situation of the central moiety from doubly bonded (R(2)N)(2)C=C=C(NR(2))(2) to a donor-acceptor description (R(2)N)(2)C-->C(H(+))(n)<--C(NR(2)) [n = 1, 2]. The atomic partial charge at the carbon donor atom does not correlate with the PA and the trend of the second PA may be quite different from the trend of the first. The trends of the first and second PA correlates quite well with the eigenvalues of the highest-lying carbon lone-pair orbitals.