Nitrosyl induces phosphorous-acid dissociation in ruthenium(ii)Electronic supplementary information (ESI) available. CCDC reference numbers 841553. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c1dt10936g
The trans -[Ru(NO)(NH 3 ) 4 (P(OH) 3 )]Cl 3 complex was synthesized by reacting [Ru(H 2 O)(NH 3 ) 5 ] 2+ with H 3 PO 3 and characterized by spectroscopic ( 31 P-NMR, δ = 68 ppm) and spectrophotometric techniques ( λ = 525 nm, = 20 L mol −1 cm −1 ; λ = 319 nm, = 773 L mol −1 cm −1 ; λ = 241 nm, = 138...
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| Main Authors | , , , , , |
|---|---|
| Format | Journal Article |
| Language | English |
| Published |
29.11.2011
|
| Online Access | Get full text |
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| Summary: | The
trans
-[Ru(NO)(NH
3
)
4
(P(OH)
3
)]Cl
3
complex was synthesized by reacting [Ru(H
2
O)(NH
3
)
5
]
2+
with H
3
PO
3
and characterized by spectroscopic (
31
P-NMR,
δ
= 68 ppm) and spectrophotometric techniques (
λ
= 525 nm,
= 20 L mol
−1
cm
−1
;
λ
= 319 nm,
= 773 L mol
−1
cm
−1
;
λ
= 241 nm,
= 1385 L mol
−1
cm
−1
;
ν
NO
+
= 1879 cm
−1
). A p
K
a
of 0.74 was determined from infrared measurements as a function of pH for the reaction:
trans
-[Ru(NO)(NH
3
)
4
(P(OH)
3
)]
3+
+ H
2
O
trans
-[Ru(NO)(NH
3
)
4
(P(O
−
)(OH)
2
)]
2+
+ H
3
O
+
. According to
31
P-NMR, IR, UV-vis, cyclic voltammetry and
ab initio
calculation data, upon deprotonation,
trans
-[Ru(NO)(NH
3
)
4
(P(OH)
3
)]
3+
yields the O-bonded linkage isomer
trans
- [Ru(NO)(NH
3
)
4
(OP(OH)
2
)]
2+
, then the
trans
-[Ru(NO)(NH
3
)
4
(OP(H)(OH)
2
)]
3+
decays to give the final products H
3
PO
3
and
trans
-[Ru(NO)(NH
3
)
4
(H
2
O)]
3+
. The dissociation of phosphorous acid from the [Ru(NO)(NH
3
)
4
]
3+
moiety is pH dependent (
k
obs
= 2.1 × 10
−4
s
−1
at pH 3.0, 25 °C).
The nitrosyl ligand in
trans
-position to P(OH)
3
increases the acidity of phosphanes inducing deprotonation of
trans
-[Ru(NO
+
)(NH
3
)
4
(P(O
−
)(OH)
2
)]
2+
which leads to isomerization to O-bonded
trans
-[Ru(NO
+
)(NH
3
)
4
(OP(OH)
2
)]
2+
. |
|---|---|
| Bibliography: | For ESI and crystallographic data in CIF or other electronic format see DOI 10.1039/c1dt10936g Electronic supplementary information (ESI) available. CCDC reference numbers 841553 |
| ISSN: | 1477-9226 1477-9234 |
| DOI: | 10.1039/c1dt10936g |