The quadruply bonded compound Mo-2(DpyF)(4) (1), where DpyF(-) is the anion
of N,N'-di(2-pyridyl)formamidine, has been prepared by ligand substitution
reactions of Mo-2(OOCCF3)(4) and either the neutral ligand, HDpyF, at ambi
ent temperature or its lithium salt, LiDpyF, under refluxing conditions. An
X-ray structural analysis shows that 1 has a paddlewheel structure with a
Mo-Mo-4 distance of 2.1108(6) Angstrom. Reaction of 1 with CoCl2 in methano
l produces the paramagnetic compound [Mo2Co(DpyF)(4)] [CoCl4]. 2MeOH (2). T
he Co(II) atom in the cation [Mo-2-Co(DpyF)(4)](2+) resides on a low-spin h
exacoordinate environment (S = 1/2) with a Co Mo separation of 2.979(6) A,
suggesting there is no direct bonding interaction between the Co and Mo ato
ms. The Mo-Mo-4 distance of 2.1096(5) Angstrom is similar to that in 1. Rea
ction of 1 and CuCl in methanol yields [Mo2Cu4(DpyF)(4)Cl-2] [CuCl2](2). 2M
eOH . Et2O (3). In the cation there are two copper atoms on each side of th
e Mot core. Each is coordinated to two pyridyl nitrogen atoms of the cis Dp
yF- ligands and loosely bridged to the other by a chloride ion. As a result
, the Cu(I) atoms are not aligned with the Mo2 unit. The Cu to Mo separatio
ns are in the range 3.003(1)-3.015(1) Angstrom, and the Mo-Mo distance of 2
.127(1) Angstrom is comparable to those in 1 and 2.