Synthesis and reactivity of dibenzometallole complexes of gold(III) and platinum(II)

Preparation and crystal structures of five organoantimony halides; (p-tolyl)antimony(III) dichloride and dibromide, diphenylantimony(III) bromide, 2′-diyl)antimony(III) chloride and bis-(2′-chlorobiphenyl-2-yl)antimony(V) trichloride

Investigations on organoantimony compounds: VI. Preparation and properties of thermally stable dialkylantimony(v) compounds of the types R2Sb(OR′)3, R2Sb(OAc)3 and R2Sb(O)OH

Oxidative addition between
(biphenyl-2,2′-diyl)phenylantimony(III),
Sb(2,2′-C
 12
H
 8
)Ph 1 and Br
 2
 or
SO
 2
Cl
 2
 gave
Sb(2,2′-C
 12
H
 8
)PhBr
 2
 2 and
Sb(2,2′-C
 12
H
 8
)PhCl
 2
 3,
respectively, while the corresponding fluoride
Sb(2,2′-C
 12
H
 8
)PhF
 2
 4 and the
thiocyanate
Sb(2,2′-C
 12
H
 8
)Ph(NCS)
 2
 5 were
obtained by metathesis reactions between 3 and KF and KSCN,
respectively Compounds 2 and 3 are isostructural but, in contrast to
the closely related SbPh
 3
X
 2
 species, individual
molecules have square-pyramidal geometry Again in contrast to
SbPh
 3
X
 2
 compounds, secondary
antimony–halogen interactions trans to the apical carbon
atom lead to solid-state dimers, implying Lewis acidity at antimony
Antimony in the thiocyanate 5 showed similar square-pyramidal geometry
with N-bonded thiocyanate groups but bridging by one thiocyanate again
gives dimers in the solid Oxidative addition between SbPhCl
 2

and tetrachloro-ortho-benzoquinone in ether solution gave the
tetrachlorocatechol analogue of 3 as a six-co-ordinate ether solvate,
SbPh(o-O
 2
C
 6
Cl
 4
)·OEt

 2
 6 If the weak bond to ether is ignored, antimony again has
square-pyramidal geometry but formation of the adduct again points to
antimony Lewis acidity A non-solvated substituted catecholate,
SbPh(o-O
 2
C
 6
H
 2
Bu
 t

 2
-3,5)Cl
 2
 8, was also synthesized but crystals
suitable for X-ray diffraction could not be obtained

New square-pyramidal organoantimony(V) compounds; crystalstructures of (biphenyl-2,2′-diyl)phenylantimony(V)dibromide, dichloride and diisothiocyanate,Sb(2,2′-C12H8)PhX2(X = Br, Cl or NCS), and of octahedralSbPh(o-O2C6Cl4)Cl2·OEt2

D. Hellwinkel

Papers

Pentaorganyle des antimons

Versuche zur darstellung spirocyclischer stiboniumsalze und antimonat-komplexe