Solvolysis Products of the Types [RhMeL
2
(Me
3
[9]aneN
3
)]
2ⴙ
and
[RuCl
3ⴚX
L
X
(Me
3
[9]aneN
3
)]
(x)ⴙ
(x ⴝ 1-2) and Preparation and Structure of
[Ru([9]aneS
3
)(Me
3
[9]aneN
3
)](CF
3
SO
3
)
2
M. Südfeld and W. S. Sheldrick
*
Bochum, Lehrstuhl für Analytische Chemie der Ruhr-Universität Bochum
Received February 7
th
, 2002
Abstract. Solvolysis of [RhMe(CF
3
SO
3
)
2
(Me
3
[9]aneN
3
)] (1)(Me
3
-
[9]aneN
3
⫽ 1,4,7-trimethyl-1,4,7-triazacyclononane) in CH
3
CN,
DMSO or pyrazole (L) leads to substitution of both trifluorome-
thylsulfonate ligands and formation of the cationic complexes
[RhMeL
2
(Me
3
[9]aneN
3
)](CF
3
SO
3
)
2
3ⴚ5. In contrast, treatment of
[RuCl
3
(Me
3
[9]aneN
3
)] (2) with Ag(CF
3
SO
3
) in a 1:3 ratio for 2h in
CH
3
CN leads to formation of the tetranuclear complex
[{RuCl
3
(Me
3
[9]aneN
3
)}
2
Ag
2
(CF
3
SO
3
)(CH
3
CN)](CF
3
SO
3
) · CH
3
CN
(6) with a novel [(RuCl
3
)
2
Ag
2
] core. More forcing conditions enable
the substitution of respectively one or two chloride ligands by
CH
3
CN (reflux 18h) or DMF (85°C, 1h) to afford
Solvolyseprodukte der Art [RhMeL
2
(Me
3
[9]aneN
3
)]
2ⴙ
und
[RuCl
3ⴚX
L
X
(Me
3
[9]aneN
3
)]
(x)ⴙ
(x ⴝ 1ⴚ2) sowie die Darstellung und Struktur von
[Ru([9]aneS
3
)(Me
3
[9]aneN
3
)](CF
3
SO
3
)
2
Inhaltsübersicht. Solvolyse von [RhMe(CF
3
SO
3
)
2
(Me
3
[9]aneN
3
)]
(1), (Me
3
[9]aneN
3
⫽ 1,4,7-Trimethyl-1,4,7-triazacyclononan), in
CH
3
CN, DMSO oder Pyrazol (L) führt zur Substitution beider
Trifluoromethylsulfonato-Liganden und Bildung der kationischen
Komplexe [RhMeL
2
(Me
3
[9]aneN
3
)](CF
3
SO
3
)
2
3⫺5. Im Gegensatz
dazu führt die zweistündige Reaktion von [RuCl
3
(Me
3
[9]aneN
3
)]
(2) mit Ag(CF
3
SO
3
) im molaren Verhältnis 1:3 in CH
3
CN zur Dar-
stellung des vierkernigen Komplexes [{RuCl
3
(Me
3
[9]aneN
3
)}
2
-
Ag
2
(CF
3
SO
3
)(CH
3
CN)](CF
3
SO
3
) · CH
3
CN (6) mit einem neuarti-
gen [(RuCl
3
)
2
Ag
2
]-Kern. Bei höheren Temperaturen können dage-
gen ein bzw. zwei Chloridliganden durch CH
3
CN (Rückfluss, 18h)
Introduction
We have demonstrated that both [RhCl(CH
3
CN)
2
-
([9]aneS
3
)](CF
3
SO
3
)
2
[1] ([9]aneS
3
⫽ 1,4,7-trithiacyclonon-
ane) and [Ru(CH
3
CN)
3
([9]aneS
3
)](CF
3
SO
3
)
2
[2, 3] provide
expedient starting materials for the synthesis of other thi-
oether half-sandwich complexes. The observed failure to
substitute the last chloride ligand in the former compound,
even in the presence of a large molar excess of Ag(CF
3
SO
3
),
*Prof. Dr. W. S. Sheldrick
Lehrstuhl für Analytische Chemie
Ruhr-Universität Bochum
D-44780 Bochum
Fax: (int. Code) ⫹ (0)234/32-14420
E-mail : shel@anachem.ruhr-uni-bochum.de
1366 WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002 0044⫺2313/02/628/1366⫺1372 $ 20.00⫹.50/0 Z. Anorg. Allg. Chem. 2002, 628, 1366⫺1372
[RuCl
2
(CH
3
CN)(Me
3
[9]aneN
3
)](CF
3
SO
3
)(7) and [RuCl(DMF)
2
-
(Me
3
[9]aneN
3
)](CF
3
SO
3
)
2
(8). The heteroleptic sandwich complex
[Ru([9]aneS
3
)(Me
3
[9]aneN
3
)](CF
3
SO
3
)
2
(9) can be prepared by re-
duction of 2 with Zn powder in acetone in the presence of 3 equiv.
of Ag(CF
3
SO
3
), followed by addition of [9]aneS
3
(1,4,7-trithiacy-
clononane). The redox potential E°(Ru
3⫹
/Ru
2⫹
)of⫹1.87 V vs
NHE for 9 is only ⫺0.12 V lower than that of the homoleptic
complex [Ru([9]aneS
3
)
2
]
2⫹
. Crystal structures are reported for 3⫺9.
Keywords: Rhodium; Ruthenium; Macrocyclic ligand complexes;
Solvolysis; Crystal structures
und DMF (85°C, 1h) unter Bildung von [RuCl
2
(CH
3
CN)(Me
3
[9]-
aneN
3
)](CF
3
SO
3
)(7) bzw. [RuCl(DMF)
2
(Me
3
[9]aneN
3
)](CF
3
SO
3
)
2
(8) ersetzt werden. Der heteroleptische Sandwich-Komplex
[Ru([9]aneS
3
)(Me
3
[9]aneN
3
)](CF
3
SO
3
)
2
(9) erhält man, nach Re-
duktion von 2 mit Zn-Pulver im Beisein von 3 Äquivalenten
Ag(CF
3
SO
3
), durch Addition von [9]aneS
3
(1,4,7-Trithiacyclono-
nan). Das Redoxpotential E°(Ru
3⫹
/Ru
2⫹
) von 1.87 V νs NHE für
9 ist nur ⫺0.12 V niedriger als für den homoleptischen Komplex
[Ru([9]aneS
3
)
2
]
2⫹
. Kristallstrukturanalysen wurden für 3⫺9 durch-
geführt.
is in accordance with the well-documented restricted ability
of macrocyclic thioethers to neutralise positive charge
through σ-donation [4]. Our recent studies [5] on the sol-
volysis and reactivity of [RhCl
3
(Me
3
[9]aneN
3
)] indicate that
the labilising trans effect of the nitrogen atoms in N,N’,N’’-
trimethyl-1,4,7-triazacyclononane, Me
3
[9]aneN
3
,iseven
weaker than for [9]aneS
3
. For instance, treatment of
[RhCl
3
(Me
3
[9]aneN
3
)] with Ag(CF
3
SO
3
) in a 1:3 molar ra-
tio at 60°C for 30 min in acetonitrile leads to formation of a
deep-yellow solution from which [{RhCl
3
(Me
3
[9]aneN
3
)}
2
-
Ag
2
(CF
3
SO
3
)(CH
3
CN)](CF
3
SO
3
) · CH
3
CN can be precipi-
tated by addition of thf. The octahedral [RhCl
3
(Me
3
[9]-
aneN
3
)] moieties remain intact and participate as six-elec-
tron donors in this tetranuclear complex with its Rh
2
Ag
2
Cl
6
central unit. Even under strongly forcing conditions (reflux,
18h) only one chloride can be replaced by CH
3
CN to afford
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