Exceptionally Long Covalent CC Bonds—A Local Vibrational Mode Study

Abstract

For decades one has strived to synthesize a compound with the longest covalent C-C bond applying predominantly steric hindrance and/or strain to achieve this goal. On the other hand electronic effects have been added to the repertoire, such as realized in the electron deficient ethane radical cation in its D3d form. Recently, negative hyperconjugation effects occurring in diamino-o-carborane analogs such as di-N,N-dimethylamino-o-carborane have been held responsible for their long C-C bonds. In this work we systematically analyzed CC bonding in a diverse set of 53 molecules including clamped bonds, highly sterically strained complexes such as diamondoid dimers, electron deficient species, and di-N,N-dimethylamino-o-carborane to cover the whole spectrum of possibilities for elongating a covalent C-C bond to the limit. As a quantitative intrinsic bond strength measure, we utilized local vibrational CC stretching force constants ka(CC) and related bond strength orders BSO n(CC), computed at the ωB97X-D/aug-cc-pVTZ level of theory. Our systematic study quantifies for the first time that whereas steric hindrance and/or strain definitely elongate a C-C bond, electronic effects can lead to even longer and weaker C-C bonds. Within our set of molecules the electron deficient ethane radical cation, in D3d symmetry, acquires the longest C-C bond with a length of 1.935 Å followed by di-N,N-dimethylamino-o-carborane with a bond length of 1.930 Å. However, the C-C bond in di-N,N-dimethylamino-o-carborane is the weakest with a BSO n value of 0.209 compared to 0.286 for the ethane radical cation; another example that the longer bond is not always the weaker bond. Based on our findings we provide new guidelines for the general characterization of CC bonds based on local vibrational CC stretching force constants and for future design of compounds with long C-C bonds.

CO bonding in hexa‐ and pentacoordinate carboxy‐neuroglobin: A quantum mechanics/molecular mechanics and local vibrational mode study

“…In their landmark paper, Zou and Cremer 138 proved that the local stretching force constant k a n (AB) reflects the intrinsic strength of the bond/interaction between two atoms A and B being described by an internal coordinate q n . In essence, LMA has advanced as a powerful analytical tool, extensively applied to a broad range of chemical systems from simple molecular systems to systems in solution 139,140 and proteins 102,141 accounting for both covalent bonds 79,88,131,138,142–152 and non‐covalent interactions 89,150,153–166 including hydrogen bonds 167–177 . Recently, a whole new scope of chemical systems were unlocked with the extension of LVM theory to periodic systems 178 …”

“…In their landmark paper, Zou and Cremer 138 proved that the local stretching force constant k a n (AB) reflects the intrinsic strength of the bond/interaction between two atoms A and B being described by an internal coordinate q n . In essence, LMA has advanced as a powerful analytical tool, extensively applied to a broad range of chemical systems from simple molecular systems to systems in solution 139,140 and proteins 102,141 accounting for both covalent bonds 79,88,131,138,[142][143][144][145][146][147][148][149][150][151][152] and noncovalent interactions 89,150,[153][154][155][156][157][158][159][160][161][162][163][164][165][166] including hydrogen bonds. [167][168][169][170][171][172][173][174][175][176]…”

Relating Bond Strength and Nature to the Thermodynamic Stability of Hypervalent Togni‐Type Iodine Compounds

“…[40] Bond length is commonly associated with bond strength. However, a caveat is appropriate; under certain circumstances, a shorter bond is not necessarily a stronger bond, as reported in the literature [40f,41] . Figure 4 shows the relationship between bond length and the intrinsic strength of the iodine bonds as reflected by k a for conformations i–iii.…”

Mechanistic Details of the Sharpless Epoxidation of Allylic Alcohols—A Combined URVA and Local Mode Study

“…LMA has been effectively used to characterize covalent bonds [86,[102][103][104][105][106][107][108][109][110][111][112][113], hydrogen bonding [114][115][116][117][118][119][120][121][122], halogen bonding [123][124][125][126][127][128][129], pnicogen bonding [129][130][131][132], chalcogen bonding [111,129,133], tetrel bonding [134] and to characterize specific properties, such as a BH• • • π interaction [135,136], an aromaticity index [137][138][139], a metal electronic parameter [120,125,138,[140][141][142]…”