Weak distance dependence of through-bond interactions in tetrahydro-4H-thiopyran-4-ylidene end-capped oligo(cyclohexylidenes); a computational survey.
Calculations on members of the oligo(cyclohexylidene) series [(n), n = 1-5)] and related tetrahydro-4H-thiopyran end-capped analogues [(n), n = 1-4)] show a strong through-bond coupling between their pi bonds and sulfur lone pairs (Lp(pi)S). This coupling is mediated by an interaction between the H(ax)-C-C-H(ax) structural sub-units and the pi bonds connecting the cyclohexyl moieties. A comparison of the length dependency of the through-bond coupling via an oligo(cyclohexylidene) and an alkane bridge [divinyl alkanes (n)] shows that oligo(cyclohexylidenes) are more efficient in mediating through-bond couplings over large distances. Oligo(cyclohexylidene) bridges exhibit molecular wire characteristics.
Havenith
Remco W A
RW
Theoretical Chemistry Group, Utrecht University, Padualaan 8, Utrecht, The Netherlands.
van Walree
Cornelis A
CA
Marsman
Alwin W
AW
van Lenthe
Joop H
JH
Jenneskens
Leonardus W
LW
D003198:Computer Simulation; D004735:Energy Transfer; D006838:Hydrocarbons / Q000737:chemistry; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D011720:Pyrazoles / Q000737:chemistry*
D006838:Hydrocarbons; D011720:Pyrazoles; C030011:carbene; C002626:thiopyrine; D008697:Methane