The complex [VCl
2
(tmen)
2

]
(tmen = N,N,N′,N
′-tetramethylethane-1,2-diamine) changes spontaneously into a
triangulo-trinuclear species
[V
3
(µ-Cl)
3
(µ
3
-Cl)
2
(tmen)
3

]
+
in solution in tetrahydrofuran
upon addition of salts of suitable counter ions. The apical
(µ
3

) chlorides can be replaced by methoxide, and
the tmen by diphosphines. Several related materials, all containing the
triangulo-V
3
X
3
(X = Cl or
Br) motif, were characterised by mass spectroscopy, X-ray diffraction
and other techniques. These clusters are antiferromagnetic both in
solution and in the solid state. Thermogravimetric analysis of
trans-[VCl
2
(tmen)
2

] and of
[V(MeOH)
6

]Cl
2
implied the formation of
similar triangulo-V
3
Cl
3
species, which
appear to be of common occurrence in vanadium(
II)
chemistry.