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E
E
E
E
Ru
R
u
O
d
n
4
r
4
n
g
|
0
HO
O
Ru
Ru
Figure 3.3
Structure of (m-oxo)tetraruthenium cluster.
.
Figure 3.4 ORTEP diagram of [Ru(N)(CH
2
SiMe
3
)
2
(m-O)
2
CrO
2
]
.
oxidation of alcohols to the corresponding aldehydes and ketones
under 1 atm of O
2
or air.
46
The heterobimetallic [(Bu
4
N)(M(N)(CH
2
SiMe
3
)
2
-
(m-O)
2
CrO
2
)] (M
¼
Ru or Os) catalyzes the selective oxidation of alcohols
with molecular O
2
(Figure 3.4).
47
A similar heterobimetallic, [PPh
4
][Ru(N)-
Me
2
(m
2
-O)
2
Pd((-)-sparteine)], prepared by the reaction of [PPh
4
]-
[Ru(N)(OH)
2
Me
2
] and Pd(OSiMe
3
)
2
((
)-sparteine) (Scheme 3.1), catalyzed the
aerobic oxidation of aryl and allylic alcohols to the corresponding carbonyl
compounds and also the rearrangement of allylic alcohols to unsaturated
aldehydes.
48
A three-dimensional microporous ruthenium(
II
,
III
) polymer complex,
[Ru
II,III
2
(H
2
TCPP)]BF
4
, where H
2
TCPP
¼
4,4
0
,4
00
,4
000
-(21H,23H)-porphine-
5,10,15,20-tetranyl)tetrakisbenzoic acid (Figure 3.5), exhibited an ecient
catalytic performance for the aerobic oxidation of a variety of alcohols.
49
A
safe, practical and selective process for the aerobic oxidation of benzylic and
allylic alcohols and also N- and S-heteroatom-containing alcohols to the
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