Coupling between two Ru(bda) catalysts bridged by a -dicyano complex
We have prepared two trimetallic complexes [{Ru(bda)(DMSO)(μ-CN)} 2 Ru(L) 4 ] (with bda = 2,2′-bipyridine-6,6′-dicarboxylate) where two {Ru(bda)} centers are bridged by a cyanide complex of the trans -Ru(L) 4 CN 2 family (with L = pyridine and 4- tert -butylpyridine). The complex [{Ru(bda)(DMSO)(μ-C...
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| Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2024-01, Vol.53 (4), p.1575-1585 |
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| creator | Abate, Pedro O Juárez, Virginia M Baraldo, Luis M |
| description | We have prepared two trimetallic complexes [{Ru(bda)(DMSO)(μ-CN)}
2
Ru(L)
4
] (with bda = 2,2′-bipyridine-6,6′-dicarboxylate) where two {Ru(bda)} centers are bridged by a cyanide complex of the
trans
-Ru(L)
4
CN
2
family (with L = pyridine and 4-
tert
-butylpyridine). The complex [{Ru(bda)(DMSO)(μ-CN)}
2
Ru(py)
4
] is fully soluble in aqueous solution and is a catalyst for the oxidation of water both chemically, using Ce(
iv
) at pH = 1 as the terminal oxidant, and electrochemically. Both reactions are first order in the complex and the resting state of the catalyst is the
[Ru
V
Ru
III
(py)
4
Ru
IV
]
2+
redox state. Electrochemical and spectroelectrochemical studies together with (TD)DFT calculations show that the coupling between the Ru(bda) fragments for the
[Ru
III
Ru
II
(py)
4
Ru
III
]
2+
and
[Ru
IV
Ru
II
(py)
4
Ru
IV
]
2+
redox states is very weak, but significant for the
[Ru
V
Ru
II
(py)
4
Ru
IV
]
2+
ion due to the orientation of the orbitals involved. This coupling affects the reactivity of the
[Ru
V
Ru
II
(py)
4
Ru
IV
]
2+
redox state, making it a much slower catalyst towards the water oxidation reaction than
[Ru
V
Ru
III
(py)
4
Ru
IV
]
2+
.
Oxidation of the central Ru ion in a tri-ruthenium complex bearing two Ru(bda) fragments results in a significant increase of its activity as a catalyst in the water oxidation reaction. |
| doi_str_mv | 10.1039/d3dt03220e |
| format | Article |
| fullrecord | <record><control><sourceid>rsc</sourceid><recordid>TN_cdi_rsc_primary_d3dt03220e</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>d3dt03220e</sourcerecordid><originalsourceid>FETCH-rsc_primary_d3dt03220e3</originalsourceid><addsrcrecordid>eNqFjjsLwjAYRYMoWB-Lu_CNOlTTpFo6-8BZ3EtelkjblCSl5t_rIDo63QPnDBehRYI3Cab5VlLpMSUEqwGKkjTL4pzQdPhlsh-jiXMPjN_NjkToeDBdW-mmBK58r1QDvjdw7VZcsjUI5lkVnHfArZalksADMIilFoE1BoSp20o9Z2h0Z5VT889O0fJ8uh0usXWiaK2umQ3F7xr951-HtjvM</addsrcrecordid><sourcetype>Publisher</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Coupling between two Ru(bda) catalysts bridged by a -dicyano complex</title><source>Royal Society Of Chemistry Journals 2008-</source><source>Alma/SFX Local Collection</source><creator>Abate, Pedro O ; Juárez, Virginia M ; Baraldo, Luis M</creator><creatorcontrib>Abate, Pedro O ; Juárez, Virginia M ; Baraldo, Luis M</creatorcontrib><description>We have prepared two trimetallic complexes [{Ru(bda)(DMSO)(μ-CN)}
2
Ru(L)
4
] (with bda = 2,2′-bipyridine-6,6′-dicarboxylate) where two {Ru(bda)} centers are bridged by a cyanide complex of the
trans
-Ru(L)
4
CN
2
family (with L = pyridine and 4-
tert
-butylpyridine). The complex [{Ru(bda)(DMSO)(μ-CN)}
2
Ru(py)
4
] is fully soluble in aqueous solution and is a catalyst for the oxidation of water both chemically, using Ce(
iv
) at pH = 1 as the terminal oxidant, and electrochemically. Both reactions are first order in the complex and the resting state of the catalyst is the
[Ru
V
Ru
III
(py)
4
Ru
IV
]
2+
redox state. Electrochemical and spectroelectrochemical studies together with (TD)DFT calculations show that the coupling between the Ru(bda) fragments for the
[Ru
III
Ru
II
(py)
4
Ru
III
]
2+
and
[Ru
IV
Ru
II
(py)
4
Ru
IV
]
2+
redox states is very weak, but significant for the
[Ru
V
Ru
II
(py)
4
Ru
IV
]
2+
ion due to the orientation of the orbitals involved. This coupling affects the reactivity of the
[Ru
V
Ru
II
(py)
4
Ru
IV
]
2+
redox state, making it a much slower catalyst towards the water oxidation reaction than
[Ru
V
Ru
III
(py)
4
Ru
IV
]
2+
.
Oxidation of the central Ru ion in a tri-ruthenium complex bearing two Ru(bda) fragments results in a significant increase of its activity as a catalyst in the water oxidation reaction.</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/d3dt03220e</identifier><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2024-01, Vol.53 (4), p.1575-1585</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27901,27902</link.rule.ids></links><search><creatorcontrib>Abate, Pedro O</creatorcontrib><creatorcontrib>Juárez, Virginia M</creatorcontrib><creatorcontrib>Baraldo, Luis M</creatorcontrib><title>Coupling between two Ru(bda) catalysts bridged by a -dicyano complex</title><title>Dalton transactions : an international journal of inorganic chemistry</title><description>We have prepared two trimetallic complexes [{Ru(bda)(DMSO)(μ-CN)}
2
Ru(L)
4
] (with bda = 2,2′-bipyridine-6,6′-dicarboxylate) where two {Ru(bda)} centers are bridged by a cyanide complex of the
trans
-Ru(L)
4
CN
2
family (with L = pyridine and 4-
tert
-butylpyridine). The complex [{Ru(bda)(DMSO)(μ-CN)}
2
Ru(py)
4
] is fully soluble in aqueous solution and is a catalyst for the oxidation of water both chemically, using Ce(
iv
) at pH = 1 as the terminal oxidant, and electrochemically. Both reactions are first order in the complex and the resting state of the catalyst is the
[Ru
V
Ru
III
(py)
4
Ru
IV
]
2+
redox state. Electrochemical and spectroelectrochemical studies together with (TD)DFT calculations show that the coupling between the Ru(bda) fragments for the
[Ru
III
Ru
II
(py)
4
Ru
III
]
2+
and
[Ru
IV
Ru
II
(py)
4
Ru
IV
]
2+
redox states is very weak, but significant for the
[Ru
V
Ru
II
(py)
4
Ru
IV
]
2+
ion due to the orientation of the orbitals involved. This coupling affects the reactivity of the
[Ru
V
Ru
II
(py)
4
Ru
IV
]
2+
redox state, making it a much slower catalyst towards the water oxidation reaction than
[Ru
V
Ru
III
(py)
4
Ru
IV
]
2+
.
Oxidation of the central Ru ion in a tri-ruthenium complex bearing two Ru(bda) fragments results in a significant increase of its activity as a catalyst in the water oxidation reaction.</description><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><sourceid/><recordid>eNqFjjsLwjAYRYMoWB-Lu_CNOlTTpFo6-8BZ3EtelkjblCSl5t_rIDo63QPnDBehRYI3Cab5VlLpMSUEqwGKkjTL4pzQdPhlsh-jiXMPjN_NjkToeDBdW-mmBK58r1QDvjdw7VZcsjUI5lkVnHfArZalksADMIilFoE1BoSp20o9Z2h0Z5VT889O0fJ8uh0usXWiaK2umQ3F7xr951-HtjvM</recordid><startdate>20240123</startdate><enddate>20240123</enddate><creator>Abate, Pedro O</creator><creator>Juárez, Virginia M</creator><creator>Baraldo, Luis M</creator><scope/></search><sort><creationdate>20240123</creationdate><title>Coupling between two Ru(bda) catalysts bridged by a -dicyano complex</title><author>Abate, Pedro O ; Juárez, Virginia M ; Baraldo, Luis M</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-rsc_primary_d3dt03220e3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><creationdate>2024</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Abate, Pedro O</creatorcontrib><creatorcontrib>Juárez, Virginia M</creatorcontrib><creatorcontrib>Baraldo, Luis M</creatorcontrib><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Abate, Pedro O</au><au>Juárez, Virginia M</au><au>Baraldo, Luis M</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Coupling between two Ru(bda) catalysts bridged by a -dicyano complex</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><date>2024-01-23</date><risdate>2024</risdate><volume>53</volume><issue>4</issue><spage>1575</spage><epage>1585</epage><pages>1575-1585</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>We have prepared two trimetallic complexes [{Ru(bda)(DMSO)(μ-CN)}
2
Ru(L)
4
] (with bda = 2,2′-bipyridine-6,6′-dicarboxylate) where two {Ru(bda)} centers are bridged by a cyanide complex of the
trans
-Ru(L)
4
CN
2
family (with L = pyridine and 4-
tert
-butylpyridine). The complex [{Ru(bda)(DMSO)(μ-CN)}
2
Ru(py)
4
] is fully soluble in aqueous solution and is a catalyst for the oxidation of water both chemically, using Ce(
iv
) at pH = 1 as the terminal oxidant, and electrochemically. Both reactions are first order in the complex and the resting state of the catalyst is the
[Ru
V
Ru
III
(py)
4
Ru
IV
]
2+
redox state. Electrochemical and spectroelectrochemical studies together with (TD)DFT calculations show that the coupling between the Ru(bda) fragments for the
[Ru
III
Ru
II
(py)
4
Ru
III
]
2+
and
[Ru
IV
Ru
II
(py)
4
Ru
IV
]
2+
redox states is very weak, but significant for the
[Ru
V
Ru
II
(py)
4
Ru
IV
]
2+
ion due to the orientation of the orbitals involved. This coupling affects the reactivity of the
[Ru
V
Ru
II
(py)
4
Ru
IV
]
2+
redox state, making it a much slower catalyst towards the water oxidation reaction than
[Ru
V
Ru
III
(py)
4
Ru
IV
]
2+
.
Oxidation of the central Ru ion in a tri-ruthenium complex bearing two Ru(bda) fragments results in a significant increase of its activity as a catalyst in the water oxidation reaction.</abstract><doi>10.1039/d3dt03220e</doi><tpages>11</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1477-9226 |
| ispartof | Dalton transactions : an international journal of inorganic chemistry, 2024-01, Vol.53 (4), p.1575-1585 |
| issn | 1477-9226 1477-9234 |
| language | |
| recordid | cdi_rsc_primary_d3dt03220e |
| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| title | Coupling between two Ru(bda) catalysts bridged by a -dicyano complex |
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