Group 5 Imido Complexes Derived from Diamido-Pyridine Ligands
Identifieur interne : 001833 ( Main/Exploration ); précédent : 001832; suivant : 001834Group 5 Imido Complexes Derived from Diamido-Pyridine Ligands
Auteurs : Stephen M. Pugh [France] ; Alexander J. Blake [France] ; Lutz H. Gade [France] ; Philip Mountford [France]Source :
- Inorganic Chemistry [ 0020-1669 ] ; 2001.
Abstract
Reaction of the vanadium(V) imide [V(NAr)Cl3(THF)] (Ar = 2,6-C6H3iPr2) with the diamino-pyridine derivative MeC(2-C5H4N)(CH2NHSiMe2tBu)2 (abbreviated as H2N‘2Npy) gave modest yields of the vanadium(IV) species [V(NAr)(H3N‘N‘ ‘Npy)Cl2] (1 where H3N‘N‘ ‘Npy = MeC(2- C5H4N)(CH2NH2)(CH2NHSiMe2tBu) in which the original H2N‘2Npy has effectively lost SiMe2tBu (as ClSiMe2tBu) and gained an H atom. Better behaved reactions were found between the heavier Group 5 metal complexes [M(NR)Cl3(py)2] (M = Nb or Ta, R = tBu or Ar) and the dilithium salt Li2[N2Npy] (where H2N2Npy = MeC(2-C5H4N)(CH2NHSiMe3)2), and these yielded the six-coordinate M(V) complexes [M(NR)Cl(N2Npy)(py)] (M = Nb, R = tBu 2; M = Ta, R = tBu 3 or Ar 4). The compounds 2−4 are fluxional in solution and undergo dynamic exchange processes via the corresponding five-coordinate homologues [M(NR)Cl(N2Npy)]. Activation parameters are reported for the complexes 2 and 3. In the case of 2, high vacuum tube sublimation afforded modest quantities of [Nb(NtBu)Cl(N2Npy)] (5). The X-ray crystal structures of the four compounds 1, 2, 3, and 4 are reported.
New Group 5 imido complexes derived from the diamido-pyridine ligand MeC(2-C5H4N)(CH2CH2NSiMe3)2 (N2Npy) are described. Among those reported are products of the reactions of Li2[N2Npy] with [M(NR)Cl3(py)2] (M = Nb, Ta; R = tBu, Ar) which gave compounds of the type shown. The X-ray structures and solution dynamics of the new compounds are described.
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DOI: 10.1021/ic0102541
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Pugh</name><affiliation wicri:level="4"><country xml:lang="fr">France</country><wicri:regionArea>Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QR, U.K.,School of Chemistry, University of Nottingham, Nottingham, NG7 2RD, U.K.,and Laboratoire de Chimie Organométallique et de Catalyse (CNRS UMR 7513), Institut Le Bel,Université Louis Pasteur, 4, rue Blaise Pascal, 67000 Strasbourg</wicri:regionArea><placeName><region type="region" nuts="2">Grand Est</region><region type="old region" nuts="2">Alsace (région administrative)</region><settlement type="city">Strasbourg</settlement></placeName><orgName type="university">Université d'Oxford</orgName></affiliation><affiliation></affiliation></author><author><name sortKey="Blake, Alexander J" sort="Blake, Alexander J" uniqKey="Blake A" first="Alexander J." last="Blake">Alexander J. 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Gade</name><affiliation wicri:level="4"><country xml:lang="fr">France</country><wicri:regionArea>Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QR, U.K.,School of Chemistry, University of Nottingham, Nottingham, NG7 2RD, U.K.,and Laboratoire de Chimie Organométallique et de Catalyse (CNRS UMR 7513), Institut Le Bel,Université Louis Pasteur, 4, rue Blaise Pascal, 67000 Strasbourg</wicri:regionArea><placeName><region type="region" nuts="2">Grand Est</region><region type="old region" nuts="2">Alsace (région administrative)</region><settlement type="city">Strasbourg</settlement></placeName><orgName type="university">Université d'Oxford</orgName></affiliation><affiliation></affiliation><affiliation></affiliation></author><author><name sortKey="Mountford, Philip" sort="Mountford, Philip" uniqKey="Mountford P" first="Philip" last="Mountford">Philip Mountford</name><affiliation wicri:level="4"><country xml:lang="fr">France</country><wicri:regionArea>Inorganic Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QR, U.K.,School of Chemistry, University of Nottingham, Nottingham, NG7 2RD, U.K.,and Laboratoire de Chimie Organométallique et de Catalyse (CNRS UMR 7513), Institut Le Bel,Université Louis Pasteur, 4, rue Blaise Pascal, 67000 Strasbourg</wicri:regionArea><placeName><region type="region" nuts="2">Grand Est</region><region type="old region" nuts="2">Alsace (région administrative)</region><settlement type="city">Strasbourg</settlement></placeName><orgName type="university">Université d'Oxford</orgName></affiliation><affiliation></affiliation><affiliation></affiliation></author></analytic><monogr></monogr><series><title level="j" type="main">Inorganic Chemistry</title><title level="j" type="abbrev">Inorg. Chem.</title><idno type="ISSN">0020-1669</idno><idno type="eISSN">1520-510X</idno><imprint><publisher>American Chemical Society</publisher><date type="e-published" when="2001-06-30">2001</date><date when="2001-07-30">2001</date><biblScope unit="vol">40</biblScope><biblScope unit="issue">16</biblScope><biblScope unit="page" from="3992">3992</biblScope><biblScope unit="page" to="4001">4001</biblScope></imprint><idno type="ISSN">0020-1669</idno></series></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0020-1669</idno></seriesStmt></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract">Reaction of the vanadium(V) imide [V(NAr)Cl3(THF)] (Ar = 2,6-C6H3iPr2) with the diamino-pyridine derivative MeC(2-C5H4N)(CH2NHSiMe2tBu)2 (abbreviated as H2N‘2Npy) gave modest yields of the vanadium(IV) species [V(NAr)(H3N‘N‘ ‘Npy)Cl2] (1 where H3N‘N‘ ‘Npy = MeC(2- C5H4N)(CH2NH2)(CH2NHSiMe2tBu) in which the original H2N‘2Npy has effectively lost SiMe2tBu (as ClSiMe2tBu) and gained an H atom. Better behaved reactions were found between the heavier Group 5 metal complexes [M(NR)Cl3(py)2] (M = Nb or Ta, R = tBu or Ar) and the dilithium salt Li2[N2Npy] (where H2N2Npy = MeC(2-C5H4N)(CH2NHSiMe3)2), and these yielded the six-coordinate M(V) complexes [M(NR)Cl(N2Npy)(py)] (M = Nb, R = tBu 2; M = Ta, R = tBu 3 or Ar 4). The compounds 2−4 are fluxional in solution and undergo dynamic exchange processes via the corresponding five-coordinate homologues [M(NR)Cl(N2Npy)]. Activation parameters are reported for the complexes 2 and 3. In the case of 2, high vacuum tube sublimation afforded modest quantities of [Nb(NtBu)Cl(N2Npy)] (5). The X-ray crystal structures of the four compounds 1, 2, 3, and 4 are reported.</div><div type="abstract">New Group 5 imido complexes derived from the diamido-pyridine ligand MeC(2-C5H4N)(CH2CH2NSiMe3)2 (N2Npy) are described. Among those reported are products of the reactions of Li2[N2Npy] with [M(NR)Cl3(py)2] (M = Nb, Ta; R = tBu, Ar) which gave compounds of the type shown. The X-ray structures and solution dynamics of the new compounds are described.</div></front></TEI><affiliations><list><country><li>France</li></country><region><li>Alsace (région administrative)</li><li>Grand Est</li></region><settlement><li>Strasbourg</li></settlement><orgName><li>Université d'Oxford</li></orgName></list><tree><country name="France"><region name="Grand Est"><name sortKey="Pugh, Stephen M" sort="Pugh, Stephen M" uniqKey="Pugh S" first="Stephen M." last="Pugh">Stephen M. Pugh</name></region><name sortKey="Blake, Alexander J" sort="Blake, Alexander J" uniqKey="Blake A" first="Alexander J." last="Blake">Alexander J. Blake</name><name sortKey="Gade, Lutz H" sort="Gade, Lutz H" uniqKey="Gade L" first="Lutz H." last="Gade">Lutz H. Gade</name><name sortKey="Mountford, Philip" sort="Mountford, Philip" uniqKey="Mountford P" first="Philip" last="Mountford">Philip Mountford</name></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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