Reaction of diethylacetylene dicarboxylate
(EtO
$_{2}$
CC≡CCO
$_{2}$
Et) with
trans-(N
$_{3})_{2}$
Ru(PMe
$_{3}$
)
$_{4}$
in THF at 25°C gave the bis-triazolato complex
(PMe
$_{3}$
)
$_{3}$
Ru[N
$_{3}$
C
$_{2}$
-(CO
$_{2}$
Et)
$_{2}$
]
$_{2}$
(1) in 41% yield. Reaction of
trans-(N
$_{3}$
)
$_{2}$
Ru(PMe
$_{3}$
)
$_{4}$
with phenylacetylene in toluene at 110
$^{\circ}$
C gave the
mixed azide acetylide complex
cis-(PMe
$_{3}$
)
$_{4}$
Ru(N
$_{3})$
(C≡CC
$_{6}$
H
$_{5})$
(2) (51%. The analogous alkynyl acetylide
cis-(PMe
$_{3}$
)
$_{4}$
Ru(N
$_{3})$
(C≡CC
$_{6}$
H
$_{4}$
C≡
CH) (3) is formed from 1,4-diethynylbenzene in 72% yield. Reaction of
trans-(N
$_{3}$
)
$_{2}$
Ru(PMe
$_{3}$
)
$_{4}$
with HC≡CSiMe
$_{3}$
in
CH
$_{2}$
Cl
$_{2}$
at 41°C gave
trans-(PMe
$_{3}$
)
$_{4}$
Ru[C≡
C(SiMe
$_{3})$
]
$_{2}$
(4) (37%. A similar
reaction in toluene at 110°C gave the dinuclear azide
[(PMe
$_{3}$
)
$_{3}$
(N
$_{3})$
Ru]
$_{2}$
(μ
$_{1,3}-$
N
$_{3}$
)
$_{2}$
(5) (30%
3,5-bis(trifluoromethyl)pyrazole (PzH) with
trans-(N
$_{3}$
)
$_{2}$
Ru(PMe
$_{3}$
)
$_{4}$
in refluxing toluene gave
[(PMe
$_{3}$
)
$_{3}$
Ru]
$_{2}$
(μ
$_{1}$
-N
$_{3}$
)
$_{3}$
][Pz·
2PzH (6). Complexes 1–6 have been characterized spectroscopically as well
as by single crystal X-ray diffraction studies.
