Charge Saturation and Neutral Substitutions in Halomethanes and Their Group 14 Analogues

A computational analysis of the charge distribution in halomethanes and their heavy analogues (MH4-nXn: M= C, Si, Ge, Sn, Pb; X = F, Cl, Br, I) as a function of n uncovers a previously unidentified saturation limit for fluorides when M ≠ C. We examine the electron densities obtained at the CCSD, MP2(full), B3PW91, and HF levels of theory for 80 molecules for four different basis sets. A previously observed substituent independent charge at F in fluoromethanes is shown to be a move toward saturation that is restricted by the low polarizability of C. This limitation fades into irrelevance for the more polarizable M central atoms such that a genuine F saturation is realized in those cases. A conceptual model leads to a function of the form [qM(n) -- qM(n)] = a[χA\u27 -- χA] + b that links the electronegativities (χ) of incoming and leaving atoms (e.g., A\u27 = X and A = H for the halogenation of MH4-nXn) and the associated charge shift at M. We show that the phenomenon in which the charge at the central atom, qM, is itself independent of n (e.g., at carbon in CH4-nBrn) is best described as an “M-neutral substitution”—not saturation. Implications of the observed X saturation and M-neutral substitutions for larger organic and inorganic halogenated molecules and polymeric materials are identified

Plane and simple: planar tetracoordinate carbon centers in small moleculesw

A class of neutral 18-electron molecules with planar tetracoordinate carbon (ptC) centers is introduced. We show computationally that when n = 3 the neutral singlet molecule C(BeH)n(BH2)4-n and other isoelectronic (18-valence electron) molecules of main group elements collapse from locally tetrahedral arrangements at the C-center to (near) planar tetracoordinate structures. For C(BeH)3BH2 and C(CH3)(BH2)Li2, for example, the tetrahedral type conformation is not even a minimum on the potential energy surface at the B3PW91, MP2(full), or CCSD levels of theory. The Mg analogue C(MgH)3BH2 of the Be system also features a completely flat global minimum (with even higher energy planar minima in both cases as well). Other neutral compounds that may prefer planar geometries are apparent, and new openings for experimental investigations and theoretical analyses of planar tetracoordinate main group systems are identified. The planar conformation persists at one center in the C(BeH)3BH2 dimer, and may be identifiable in higher order clusters of ptC molecules as well

Shorter Still: Compressing C-C Single Bonds

How short can a C-C single bond get? The bonding in a set of molecules that are related structurally to previously synthesized or theoretically examined systems with short C-C bonds is investigated. According to calculations, a single C-C bond could be compressed to 1.313 A! To the best of our knowledge, this is the shortest single C-C bond reported to date. This shortening is a consequence of a change in the C-C-C bond angle, θ, to minimize strain in the cages and an effort to offset the tension in the surrounding bridges