478
H. Hirao
Mo
O
S
S
O
S Cu
Mo
O
S
S
O
S Cu
C
Mo
O
S
S
O
S Cu
C
O
S
S
O
S
Mo
O
S
S
O
S
C O
Cu
S
Mo
O
S
S
O
S
C O
Cu
S
Mo
O
S
S
O
H
S
C O
Cu
S
Mo
O
S
S
S Cu
S
Mo
O
S
S
O
S Cu
S
H
H
CO
O C O
H 2 O
2H + , 2e -
(i) thiocarbonate
formation
(ii) CO 2 release
(iii) H 2 O coordination
& oxidation
VI
IV
IV
(thiocarbonate)
Fig. 15 Our proposed mechanism of the CO oxidation catalyzed by Mo–Cu CODH (Reprinted
with permission from [78]. Copyright 2018 Royal Society of Chemistry)
(Fig. 15): (i) thiocarbonate formation, (ii) CO 2 release, and (iii) H 2 O coordination
and oxidation.
5 Studies of MOFs
5.1 QM/MM Studies of MOFs
We have recently made new attempts to study chemical reactions occurring in MOFs
using QM/MM and MM [84–88]. MOFs are similar to metalloenzymes in the sense
that both have metal ions and organic groups as building blocks, although their structures are fundamentally different. QM/MM has been applied to a number of reactions
that occur in metalloenzymes and other enzymes, but by comparison, applications
of QM/MM to MOF-catalyzed reactions had been few and far between.