A theoretical study of the H n F4−n Si:N-base (n = 1–4) tetrel-bonded complexes

Hexacoordinated Tetrel‐Bonded Complexes between TF4 (T=Si, Ge, Sn, Pb) and NCH: Competition between σ‐ and π‐Holes

“…These tetrel bonds differ a bit from the others in this set of noncovalent bonds primarily in that the central atom is typically covalently bonded to four substituents, as compared to only one for a halogen bond or as many as three for a pnicogen bond. It is known for example, that the tetrel bond formed by a TR 4 molecule (T = tetrel atom) is strengthened by increasing electron-withdrawing capacity of the R substituent, [28][29][30] as well as increasing size of the T atom (i. e. C < Si < Ge). Despite any barriers to their formation, these tetrel bonds occur widely and are of great import in a number of chemical and biological processes.…”

“…[16][17][18][19][20][21] There is a rapidly growing literature [22][23][24][25][26][27] that has provided a wealth of insights into the chemical and physical phenomena that underlie tetrel bonds. It is known for example, that the tetrel bond formed by a TR 4 molecule (T = tetrel atom) is strengthened by increasing electron-withdrawing capacity of the R substituent, [28][29][30] as well as increasing size of the T atom (i. e. C < Si < Ge). [31][32][33][34] This strengthening is amplified when either molecule acquires an electric charge.…”

Halogen, Chalcogen, and Pnicogen Bonding Involving Hypervalent Atoms

“…After many decades of intense study, the hydrogen bond (HB) has rewarded researchers with a rich trove of interesting and useful insights into its nature. Although assumed for many years to be a unique sort of interaction, more recent work has demonstrated that the HB has a number of noncovalent bonding sisters . The replacement of the bridging proton by any of a host of electronegative atoms from the right side of the periodic table yields an attractive force with many parallels to the HB.…”

“…Although assumed for many years to be au nique sort of interaction, more recent work has demonstrated that the HB has an umbero fn oncovalent bonding sisters. [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21] The replacement of the bridging protonb ya ny of ah ost of electronegative atoms from the right side of the periodic table yields an attractivef orce with many parallels to the HB. This group of bonds usually assumes the name of the family of the bridging atom, whether halogen, chalcogen, pnicogen, or tetrel, and share many features with one another.F or example,t he HB is held together in part by aC oulombic attraction between the partially positive bridging Ha nd ap artial negative charge on the proton acceptor atom.…”

Ability of IR and NMR Spectral Data to Distinguish between a Tetrel Bond and a Hydrogen Bond

“…The term "tetrel bond" was first coined in 2013 17 where it was related to atoms below C in this family of the periodic table. And indeed it is to these heavier atoms that most previous work has been devoted [18][19][20][21][22][23][24][25][26] . In the case of the C atom, its ability to engage in a TB has typically been amplified by adding a number of electron-withdrawing substituents like F [27][28][29] rather than considering a CH3 group itself.…”