Bimetal lic reagents fea tur ing one main-group el e ment and a first-row tran si tion metal
cen tre have been the fo cus of ex ten sive re search due to their nu mer ous ap pli ca tions.
In par tic u lar, the re gios e lec tive ac ti va tion of C–H bonds us ing bimetal lic com plexes
has at tracted sig nif i cant at ten tion be cause of the ubiq ui tous pres ence of these bonds
in or ganic com pounds, as well as the mild re ac tion con di tions and good atom econ -
omy that these com plexes of fer. How ever, their re ac tiv ity is of ten not well un der -
stood, which has prompted den sity func tional the ory (DFT) stud ies to shed light into
the un der ly ing mech a nisms. In this chap ter, we re view some of the chal lenges as so ci -
ated with the com pu ta tional mod el ling of bimetal lic C–H met al la tion processes (and
re lated re ac tions) which may com pro mise the con clu sions drawn from these stud ies.
Some il lus tra tive ex am ples are pro vided to high light, for in stance, the of ten-ne -
glected ef fects that silent donors and non-in no cent sol vents can have on chem i cal
spe ci a tion and lig and scram bling with bimetal lic sys tems, which in ti mately de ter -
mine their chem i cal re ac tiv ity. In ad di tion, we dis cuss the im por tance of choos ing an
ap pro pri ate the o ret i cal model when deal ing with ion-pair species and out line some
com pu ta tional tools to get fur ther in sights into rel e vant in ter ac tions in flu enc ing sta -
bil ity, while also ex am in ing their po ten tial uses and mis uses. Fi nally, we dis cuss an
ap proach that com bines hy brid sol va tion mod els and mi cro ki netic mod el ling to cor -
rectly de scribe the in flu ence of co or di nat ing sol vents on chem i cal re ac tiv ity.
