gold(III) benzocarbaporphyrin 102-Au [129], silver(III) tropoporphyrin 103-Ag
[91],
palladium(II)
1,3-naphthiporphyrin
104-Pd
[90],
palladium
(II) 1,4-naphthiporphyrin 105-Pd [130], palladium(II) meso-anthriporphyrin 106Pd [131], palladium(II) pyreniporphyrin 107-Pd [132], and phosphorus(V)
phenathriporphyrin 108-P [133].
On the other hand, several expanded and contracted porphyrins which incorporate
pincer motifs containing a meta-phenylene or pyridine moiety (Scheme 55), such as
subpyriporphyrin 109 [134], dithia-m-benzisapphyrin 110 [139], the dithia analogue
of meso-alkylidenyl-m-benzisapphyrins 111 [138], m-benzihexaphyrins
(1.0.0.1.0.0) 112 [135, 136], and dipyrihexaphyrin (1.1.1.1.1.1) 113 [137], can be
potentially applied as promising ligands in this area, as exemplified by in-plane
thorium(IV), uranium(IV), and neptunium(IV) dipyriamethyrin complexes 114-Ac
[140, 141].
S
N
N
S
109
110
111
N
NH
N
HN
Ar
Ar
Ar
Ar
S
N
N
S
Ar
Ar
R
R
R
R
Ar
Ar
EtO 2 C
Me
CO 2 Et
Me
CO 2 Et
Me
EtO 2 C
Me
N
N
N
CO 2 Et
EtO 2 C
EtO 2 C
CO 2 Et
N
N
N
EtO 2 C
CO 2 Et
CO 2 Et
EtO 2 C
Ar
Ar
112
N HN
N
Ar
Ar
Ar
113
N
N
N
N
N
N
Ar
Ar
Ac
X
X
Ac = Th(IV), U(IV), Np(IV)
114-Ac
Scheme 55 Select examples of contracted and expanded porphyrinoids, containing a metaphenylene or pyridine moiety [134–141]
A Pincer Motif Etched into a meta-Benziporphyrin Frame
221