The organomercurials
[HgCl{C6H3(CHO)2-2,5}]
(1) and
[Hg{C6H3(CHO)2-2,5}2]
(2) have
been prepared by mercuriation of terephthaldehyde. Palladium
complexes [PdCl{C6H3(CHO)2-2,5}(N-N)] (N-N =
N,N,N‘,N‘-tetramethylethylenediamine
(tmeda) (3) or 2,2‘-bipyridine (bpy) (3‘)) or
trans-[PdCl{C6H3(CHO)2-2,5}(PPh3)2]·H2O
(4) have been obtained
by reacting
(Me4N)2[Pd2Cl6]
or
trans-[PdCl2(PPh3)2],
respectively, with 1 or 2. The
reaction
of potassium permanganate with complexes 3 and 3‘
or mercurial 1 results in the selective
oxidation of the 5-formyl substituent affording
[PdCl{C6H3(CHO)-2-(CO2H)-5}(N-N)]
(N-N
= tmeda (5), bpy (5‘)) or, respectively, a
mixture whose major component is the fully oxidized
[HgCl{C6H3(CO2H)2-2,5}]
(7) or a mixture of isomers
[HgCl{C6H3(CHO)-2-(CO2H)-5}]/[HgCl{C6H3(CO2H)-2-(CHO)}]
(8a/8b) depending on the molar ratio of the
reagents. The reaction
of mixtures containing 7 or 8 with
trans-[PdCl2(PPh3)2]
give pure
trans-[PdCl{C6H3(CO2H)2-2,5}(PPh3)2] (9) or
trans-[PdCl{C6H3(CHO)-2-(CO2H)-5}(PPh3)2]
(10), respectively. Complexes
3 and 3‘ react with amines and
NaClO4·H2O or
Tl(CF3SO3) to give, depending of the
reaction
conditions, cyclopalladated
The mercurial 1 reacts with hydroxylamine to
give
the mercuriated oxime
[HgCl{C6H3(CHNOH)2-2,5}]
(14), which reacts with
(Me4N)2[Pd2Cl6] to give the cyclopalladated
From 15 some derivatives have been prepared.
Complex 3 reacts with NH2OMe to
give
The imine
C6H4(CHNTo)2-1,4
(To
= C6H4Me-4) reacts with
palladium(II) acetate to give the dipalladated
Hydrolysis of 20 in the
presence
of potassium bromide and bpy results in the formation of
[C6H2{PdBr(bpy)}2-1,4-(CHO)2-2,5] (21), from which
[C6H2{Pd(PPh3)(bpy)}2-1,4-(CHO)2-2,5](CF3SO3)2
(22) can be prepared.
The structures of
9·Me2CO·1.5MeOH,
10·2CH2Cl2
(R =
C6H4NH2-4) (12c‘)
have been determined by X-ray crystallography.
