Synthesis of Dinuclear Mo−Fe Hydride Complexes and Catalytic Silylation of N 2
Two transition‐metal atoms bridged by hydrides may represent a useful structural motif for N 2 activation by molecular complexes and the enzyme active site. In this study, dinuclear Mo IV ‐Fe II complexes with bridging hydrides, Cp R Mo(PMe 3 )(H)(μ‐H) 3 FeCp* ( 2 a ; Cp R =Cp*=C 5 Me 5 , 2 b ; Cp R...
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| Veröffentlicht in: | Chemistry : a European journal 2020-08, Vol.26 (43), p.9537-9546 |
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| creator | Ishihara, Kodai Araki, Yuna Tada, Mizuki Takayama, Tsutomu Sakai, Yoichi Sameera, W. M. C. Ohki, Yasuhiro |
| description | Two transition‐metal atoms bridged by hydrides may represent a useful structural motif for N
2
activation by molecular complexes and the enzyme active site. In this study, dinuclear Mo
IV
‐Fe
II
complexes with bridging hydrides, Cp
R
Mo(PMe
3
)(H)(μ‐H)
3
FeCp* (
2 a
; Cp
R
=Cp*=C
5
Me
5
,
2 b
; Cp
R
=C
5
Me
4
H), were synthesized via deprotonation of Cp
R
Mo(PMe
3
)H
5
(
1 a
; Cp
R
=Cp*,
1 b
; Cp
R
=C
5
Me
4
H) by Cp*FeN(SiMe
3
)
2
, and they were characterized by spectroscopy and crystallography. These Mo−Fe complexes reveal the shortest Mo−Fe distances ever reported (2.4005(3) Å for
2 a
and 2.3952(3) Å for
2 b
), and the Mo−Fe interactions were analyzed by computational studies. Removal of the terminal Mo−H hydride in
2 a
–
2 b
by [Ph
3
C]
+
in THF led to the formation of cationic THF adducts [Cp
R
Mo(PMe
3
)(THF)(μ‐H)
3
FeCp*]
+
(
3 a
; Cp
R
=Cp*,
3 b
; Cp
R
=C
5
Me
4
H). Further reaction of
3 a
with LiPPh
2
gave rise to a phosphido‐bridged complex Cp*Mo(PMe
3
)(μ‐H)(μ‐PPh
2
)FeCp* (
4
). A series of Mo−Fe complexes were subjected to catalytic silylation of N
2
in the presence of Na and Me
3
SiCl, furnishing up to 129±20 equiv of N(SiMe
3
)
3
per molecule of
2 b
. Mechanism of the catalytic cycle was analyzed by DFT calculations. |
| doi_str_mv | 10.1002/chem.202000104 |
| format | Article |
| fullrecord | <record><control><sourceid>crossref</sourceid><recordid>TN_cdi_crossref_primary_10_1002_chem_202000104</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>10_1002_chem_202000104</sourcerecordid><originalsourceid>FETCH-LOGICAL-c844-ab04920a0166c72607b333f535f5444926f1410f83d0d8074f3d0392eddc43dd3</originalsourceid><addsrcrecordid>eNo9kMtKxDAYhYMoOI5uXecFWv_kT9J2KdVxhPECM_uSyYWJ9DI0FewbuPYRfRJbFFfnwLksPkKuGaQMgN-Yg2tSDhwAGIgTsmCSswQzJU_JAgqRJUpicU4uYnybOoVCXJDX7dgOBxdDpJ2nd6F9N7XTPX3qvj-_Vo6uR9sH62jZNcfafbhIdWtpqQddj0MwdBvqsdZD6Np5_0z5JTnzuo7u6k-XZLe635XrZPPy8FjebhKTC5HoPYiCgwamlMm4gmyPiF6i9FKIKVKeCQY-Rws2h0z4yWDBnbVGoLW4JOnvrem7GHvnq2MfGt2PFYNqxlHNOKp_HPgDnzxStQ</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Synthesis of Dinuclear Mo−Fe Hydride Complexes and Catalytic Silylation of N 2</title><source>Wiley Online Library All Journals</source><creator>Ishihara, Kodai ; Araki, Yuna ; Tada, Mizuki ; Takayama, Tsutomu ; Sakai, Yoichi ; Sameera, W. M. C. ; Ohki, Yasuhiro</creator><creatorcontrib>Ishihara, Kodai ; Araki, Yuna ; Tada, Mizuki ; Takayama, Tsutomu ; Sakai, Yoichi ; Sameera, W. M. C. ; Ohki, Yasuhiro</creatorcontrib><description>Two transition‐metal atoms bridged by hydrides may represent a useful structural motif for N
2
activation by molecular complexes and the enzyme active site. In this study, dinuclear Mo
IV
‐Fe
II
complexes with bridging hydrides, Cp
R
Mo(PMe
3
)(H)(μ‐H)
3
FeCp* (
2 a
; Cp
R
=Cp*=C
5
Me
5
,
2 b
; Cp
R
=C
5
Me
4
H), were synthesized via deprotonation of Cp
R
Mo(PMe
3
)H
5
(
1 a
; Cp
R
=Cp*,
1 b
; Cp
R
=C
5
Me
4
H) by Cp*FeN(SiMe
3
)
2
, and they were characterized by spectroscopy and crystallography. These Mo−Fe complexes reveal the shortest Mo−Fe distances ever reported (2.4005(3) Å for
2 a
and 2.3952(3) Å for
2 b
), and the Mo−Fe interactions were analyzed by computational studies. Removal of the terminal Mo−H hydride in
2 a
–
2 b
by [Ph
3
C]
+
in THF led to the formation of cationic THF adducts [Cp
R
Mo(PMe
3
)(THF)(μ‐H)
3
FeCp*]
+
(
3 a
; Cp
R
=Cp*,
3 b
; Cp
R
=C
5
Me
4
H). Further reaction of
3 a
with LiPPh
2
gave rise to a phosphido‐bridged complex Cp*Mo(PMe
3
)(μ‐H)(μ‐PPh
2
)FeCp* (
4
). A series of Mo−Fe complexes were subjected to catalytic silylation of N
2
in the presence of Na and Me
3
SiCl, furnishing up to 129±20 equiv of N(SiMe
3
)
3
per molecule of
2 b
. Mechanism of the catalytic cycle was analyzed by DFT calculations.</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.202000104</identifier><language>eng</language><ispartof>Chemistry : a European journal, 2020-08, Vol.26 (43), p.9537-9546</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c844-ab04920a0166c72607b333f535f5444926f1410f83d0d8074f3d0392eddc43dd3</citedby><cites>FETCH-LOGICAL-c844-ab04920a0166c72607b333f535f5444926f1410f83d0d8074f3d0392eddc43dd3</cites><orcidid>0000-0001-5573-2821</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27924,27925</link.rule.ids></links><search><creatorcontrib>Ishihara, Kodai</creatorcontrib><creatorcontrib>Araki, Yuna</creatorcontrib><creatorcontrib>Tada, Mizuki</creatorcontrib><creatorcontrib>Takayama, Tsutomu</creatorcontrib><creatorcontrib>Sakai, Yoichi</creatorcontrib><creatorcontrib>Sameera, W. M. C.</creatorcontrib><creatorcontrib>Ohki, Yasuhiro</creatorcontrib><title>Synthesis of Dinuclear Mo−Fe Hydride Complexes and Catalytic Silylation of N 2</title><title>Chemistry : a European journal</title><description>Two transition‐metal atoms bridged by hydrides may represent a useful structural motif for N
2
activation by molecular complexes and the enzyme active site. In this study, dinuclear Mo
IV
‐Fe
II
complexes with bridging hydrides, Cp
R
Mo(PMe
3
)(H)(μ‐H)
3
FeCp* (
2 a
; Cp
R
=Cp*=C
5
Me
5
,
2 b
; Cp
R
=C
5
Me
4
H), were synthesized via deprotonation of Cp
R
Mo(PMe
3
)H
5
(
1 a
; Cp
R
=Cp*,
1 b
; Cp
R
=C
5
Me
4
H) by Cp*FeN(SiMe
3
)
2
, and they were characterized by spectroscopy and crystallography. These Mo−Fe complexes reveal the shortest Mo−Fe distances ever reported (2.4005(3) Å for
2 a
and 2.3952(3) Å for
2 b
), and the Mo−Fe interactions were analyzed by computational studies. Removal of the terminal Mo−H hydride in
2 a
–
2 b
by [Ph
3
C]
+
in THF led to the formation of cationic THF adducts [Cp
R
Mo(PMe
3
)(THF)(μ‐H)
3
FeCp*]
+
(
3 a
; Cp
R
=Cp*,
3 b
; Cp
R
=C
5
Me
4
H). Further reaction of
3 a
with LiPPh
2
gave rise to a phosphido‐bridged complex Cp*Mo(PMe
3
)(μ‐H)(μ‐PPh
2
)FeCp* (
4
). A series of Mo−Fe complexes were subjected to catalytic silylation of N
2
in the presence of Na and Me
3
SiCl, furnishing up to 129±20 equiv of N(SiMe
3
)
3
per molecule of
2 b
. Mechanism of the catalytic cycle was analyzed by DFT calculations.</description><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNo9kMtKxDAYhYMoOI5uXecFWv_kT9J2KdVxhPECM_uSyYWJ9DI0FewbuPYRfRJbFFfnwLksPkKuGaQMgN-Yg2tSDhwAGIgTsmCSswQzJU_JAgqRJUpicU4uYnybOoVCXJDX7dgOBxdDpJ2nd6F9N7XTPX3qvj-_Vo6uR9sH62jZNcfafbhIdWtpqQddj0MwdBvqsdZD6Np5_0z5JTnzuo7u6k-XZLe635XrZPPy8FjebhKTC5HoPYiCgwamlMm4gmyPiF6i9FKIKVKeCQY-Rws2h0z4yWDBnbVGoLW4JOnvrem7GHvnq2MfGt2PFYNqxlHNOKp_HPgDnzxStQ</recordid><startdate>20200803</startdate><enddate>20200803</enddate><creator>Ishihara, Kodai</creator><creator>Araki, Yuna</creator><creator>Tada, Mizuki</creator><creator>Takayama, Tsutomu</creator><creator>Sakai, Yoichi</creator><creator>Sameera, W. M. C.</creator><creator>Ohki, Yasuhiro</creator><scope>AAYXX</scope><scope>CITATION</scope><orcidid>https://orcid.org/0000-0001-5573-2821</orcidid></search><sort><creationdate>20200803</creationdate><title>Synthesis of Dinuclear Mo−Fe Hydride Complexes and Catalytic Silylation of N 2</title><author>Ishihara, Kodai ; Araki, Yuna ; Tada, Mizuki ; Takayama, Tsutomu ; Sakai, Yoichi ; Sameera, W. M. C. ; Ohki, Yasuhiro</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c844-ab04920a0166c72607b333f535f5444926f1410f83d0d8074f3d0392eddc43dd3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Ishihara, Kodai</creatorcontrib><creatorcontrib>Araki, Yuna</creatorcontrib><creatorcontrib>Tada, Mizuki</creatorcontrib><creatorcontrib>Takayama, Tsutomu</creatorcontrib><creatorcontrib>Sakai, Yoichi</creatorcontrib><creatorcontrib>Sameera, W. M. C.</creatorcontrib><creatorcontrib>Ohki, Yasuhiro</creatorcontrib><collection>CrossRef</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Ishihara, Kodai</au><au>Araki, Yuna</au><au>Tada, Mizuki</au><au>Takayama, Tsutomu</au><au>Sakai, Yoichi</au><au>Sameera, W. M. C.</au><au>Ohki, Yasuhiro</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Synthesis of Dinuclear Mo−Fe Hydride Complexes and Catalytic Silylation of N 2</atitle><jtitle>Chemistry : a European journal</jtitle><date>2020-08-03</date><risdate>2020</risdate><volume>26</volume><issue>43</issue><spage>9537</spage><epage>9546</epage><pages>9537-9546</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>Two transition‐metal atoms bridged by hydrides may represent a useful structural motif for N
2
activation by molecular complexes and the enzyme active site. In this study, dinuclear Mo
IV
‐Fe
II
complexes with bridging hydrides, Cp
R
Mo(PMe
3
)(H)(μ‐H)
3
FeCp* (
2 a
; Cp
R
=Cp*=C
5
Me
5
,
2 b
; Cp
R
=C
5
Me
4
H), were synthesized via deprotonation of Cp
R
Mo(PMe
3
)H
5
(
1 a
; Cp
R
=Cp*,
1 b
; Cp
R
=C
5
Me
4
H) by Cp*FeN(SiMe
3
)
2
, and they were characterized by spectroscopy and crystallography. These Mo−Fe complexes reveal the shortest Mo−Fe distances ever reported (2.4005(3) Å for
2 a
and 2.3952(3) Å for
2 b
), and the Mo−Fe interactions were analyzed by computational studies. Removal of the terminal Mo−H hydride in
2 a
–
2 b
by [Ph
3
C]
+
in THF led to the formation of cationic THF adducts [Cp
R
Mo(PMe
3
)(THF)(μ‐H)
3
FeCp*]
+
(
3 a
; Cp
R
=Cp*,
3 b
; Cp
R
=C
5
Me
4
H). Further reaction of
3 a
with LiPPh
2
gave rise to a phosphido‐bridged complex Cp*Mo(PMe
3
)(μ‐H)(μ‐PPh
2
)FeCp* (
4
). A series of Mo−Fe complexes were subjected to catalytic silylation of N
2
in the presence of Na and Me
3
SiCl, furnishing up to 129±20 equiv of N(SiMe
3
)
3
per molecule of
2 b
. Mechanism of the catalytic cycle was analyzed by DFT calculations.</abstract><doi>10.1002/chem.202000104</doi><tpages>10</tpages><orcidid>https://orcid.org/0000-0001-5573-2821</orcidid></addata></record> |
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| issn | 0947-6539 1521-3765 |
| language | eng |
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| source | Wiley Online Library All Journals |
| title | Synthesis of Dinuclear Mo−Fe Hydride Complexes and Catalytic Silylation of N 2 |
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