Chemistry Reference
In-Depth Information
Table 6.43
Simple aryloxides of silver
Bond length ( A)
Bond angle (
Ž
)
Compound
Aryloxide
M-O
M-O-Ar
Ref.
[Ag(OAr)]
polymeric structure,
tbp silver,
Ag - phenyl carbon
interaction
OC
6
H
2
Cl
3
-2,4,6
2.317 (3) - 2.543 (3)
i
[
AgOAr
PPh
3
2
]
trigonal planar Ag with
capping Cl
OC
6
H
2
Cl
3
-2,4,6
2.235 (4)
125
ii
i
G. Smith, E.J. O'Reilly, B.J. Reynolds, C.H.L. Kennard, and T.C.W. Mak,
J. Organomet. Chem.
,
331
, 275 (1987).
ii
G. Wulfsberg, D. Jackson, W. Ilsley, S. Dou, A. Weiss, and J. Gagliardi,
Z. Naturforsch. A
,
47
, 75 (1992).
Table 6.44
Simple aryloxides of gold
Bond length ( A)
Bond angle (
Ž
)
Compound
Aryloxide
M-O
M-O-Ar
Ref.
[Au(OAr)
PPh
3
]
OC
6
Cl
5
2.047 (5)
131
i
[Au(OAr)
PPh
3
]
OC
6
H
4
Br-2
2.025 (8)
126
ii
2.019 (8)
129
[Au(OAr)
PPh
3
]
HOAr
OC
6
H
4
Me-4
2.033 (9)
125
iii
cis
-[Au(OAr)Me
2
PPh
3
]
6
H
5
2.09 (1)
123
iv
square planar Au
i
L.G. Kuz'mina and Yu.T. Struchkov,
Koord. Khim.
,
14
, 1262 (1988).
ii
L.G. Kuz'mina, O.Yu Burtseva, N.V. Dvortsova, M.A. Porai-Koshits, and E.I. Smyslova,
Koord.
Khim.
,
15
, 773 (1989).
iii
L.G. Kuz'mina, Yu.T. Struchkov, and E.I. Smyslova,
Koord. Khim.
,
15
, 368 (1989).
iv
T. Sone, M. Iwata, N. Kasuga, and S. Komiya,
Chem. Lett.
, 1949 (1991).
[Cu(
3
-OC
6
H
4
-
2
-CH
2
CH
D
CH
2
-2)]
4
have been obtained from mesityl-copper and
fully characterized.
513
,
514
The 2,6-diphenylphenoxide adopts a planar cluster with two-
coordinate copper. In the 2-allylphenoxide, chelation of the olefinic group leads to
four-coordinate copper. The cubic cluster contains
3
-aryloxide oxygens with one very
long Cu-O distance. In the presence of suitable ligands, more manageable, discrete
Cu(
I
) aryloxides are formed. One common structural motif is the dimeric [L
n
Cu(
2
-
OAr)
2
CuL
m
] species. Both three- and four-coordinate copper are observed, depending
on the nature of L and the steric requirements of Ar. Examples include the carbonyls
[(C O) C u (
2
-OAr)
2
Cu(CO)] (ArO D OC
6
H
3
Ph
2
-2,6,
513
OC
6
H
2
Bu
t
3
-2,4,6, and OC
6
H
2
Me
3
-
2,4,6
515
) and isocyanide [(RNC)
2
Cu(
2
-OPh)
2
Cu(CNR)
2
]
516
(R D C
6
H
4
Me-4). The
monomeric, three-coordinate complex [Cu(OC
6
H
2
Bu
t
3
-2,4,6)(CNC
6
H
4
Me-4)
2
]forms
for the bulkier aryloxide.
511
,
517
The ligand PPh
3
can form a variety of structures ranging
from cubic [Cu
4
(
3
-OPh)
4
(PPh
3
)
4
]
518
to dinuclear [(Ph
3
P)
2
Cu(
2
-OPh)
2
Cu(PPh
3
)
2
].
512
Interestingly two examples of mixed three-four-coordinate compounds [(Ph
3
P)Cu(
2
-
OAr)
2
Cu(PPh
3
)
2
] (OAr D OPh,
518
OC
6
H
4
Me-4
519
) have been characterized.
