inorganic chemistry

OR

OR

RO

RO

RO

OR

OC

OC

CO

Re N

RO OR

OC

OC

OC

Br

Re N

OC CO

R = C 6 H 13 , C 12 H 25

Br Re CO

NN

N

OC

L =

R = -(CH 2 ) 3 CH 3 , -(CH 2 ) 7 CH 3 , -(CH 2 ) 11 CH 3 L =

N

N

N

CO

CI

CI

CI

CI

CO

CO

CO

OC

OC

CO

CO

CO CO

OC L Re

Re Re

Re

LL

L

OC

N

CO

CO

Br

Re

N

N

CI PPh^2

PPh 2

Ph 2 P

Ph 2

P

OC

CO

N Pd

Pd

N

N

N

N

N

N

Re N

CICO

CO

CO

Re

OC

OC

CO

Re N

OC

CO

CO

N Re

RO OR

OC

CO

CO

N Re

(a) (b)

(d)

(c)

CO

FIG. 14. Rhenium molecular rectangle (a), square (b), triangle
(c), and Re/Pd square (d).

NN

OC Re

OC CO

P

Ph 2

Ph 2

N

N

P Re

OC CO

CO

2+

N N

OC Re

hn(l> 330 nm) 30 min

in CH 3 CN

–CO OC CO

P

Ph 2

Ph 2

N

N

P Re

OC

Y= 100%

Y≈30%

CO

NCCH 3

2+

N

N

H 3 CCN Re

OC CO

P

Ph 2

Ph 2

N

N

P Re

OC CO

NCCH 3

2+

hn(l> 330 nm) 15 h

in CH 3 CN

–CO

SCHEME 5. Photochemical ligand substitution reactions for
introducing replaceable solvent molecules (CH 3 CN).

162 HIROYUKI TAKEDAet al.