A combined
experimental and computational study of the structure
and reactivity of two [RuZn
2
Me
2
] complexes,
neutral [Ru(PPh
3
)(Ph
2
PC
6
H
4
)
2
(ZnMe)
2
] (
2
) and cationic [Ru(PPh
3
)
2
(Ph
2
PC
6
H
4
)(ZnMe)
2
][BAr
F
4
] ([BAr
F
4
] = [B{3,5-(CF
3
)
2
C
6
H
3
}
4
]) (
3
), is presented. Structural and computational
analyses indicate these complexes are best formulated as containing
discrete ZnMe ligands in which direct Ru–Zn bonding is complemented
by weaker Zn···Zn interactions. The latter are stronger
in
2
, and both complexes exhibit an additional Zn···C
aryl
interaction with a cyclometalated phosphine ligand, this
being stronger in
3
. Both
2
and
3
show diverse reactivity under thermolysis and with Lewis bases (P
n
Bu
3
, PCy
3
, and IMes). With
3
, all three Lewis bases result in the loss of [ZnMe]
+
.
In contrast,
2
undergoes PPh
3
substitution
with P
n
Bu
3
, but with IMes, loss of ZnMe
2
occurs to form [Ru(PPh
3
)(C
6
H
4
PPh
2
)(C
6
H
4
PPhC
6
H
4
Zn(IMes))H] (
7
). The reaction of
3
with H
2
affords the cationic trihydride complex [Ru(PPh
3
)
2
(ZnMe)
2
(H)
3
][BAr
F
4
] (
12
). Computational analyses indicate
that both
12
and
7
feature bridging hydrides
that are biased toward Ru over Zn.