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Diimidokomplexe [M(NR)2(PMe3)2(L)] des vierwertigen Molybdäns und Wolframs: Struktur, Moleküldynamik und Aktivierung π‐acider Liganden
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| Zeitschriftentitel: | Chemische Berichte |
|---|---|
| Personen und Körperschaften: | , , |
| In: | Chemische Berichte, 127, 1994, 10, S. 1827-1835 |
| Format: | E-Article |
| Sprache: | Englisch |
| veröffentlicht: |
Wiley
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| Schlagwörter: |
| author_facet |
Radius, Udo Sundermeyer, Jörg Pritzkow, Hans Radius, Udo Sundermeyer, Jörg Pritzkow, Hans |
|---|---|
| author |
Radius, Udo Sundermeyer, Jörg Pritzkow, Hans |
| spellingShingle |
Radius, Udo Sundermeyer, Jörg Pritzkow, Hans Chemische Berichte Diimidokomplexe [M(NR)2(PMe3)2(L)] des vierwertigen Molybdäns und Wolframs: Struktur, Moleküldynamik und Aktivierung π‐acider Liganden Inorganic Chemistry |
| author_sort |
radius, udo |
| spelling |
Radius, Udo Sundermeyer, Jörg Pritzkow, Hans 0009-2940 Wiley Inorganic Chemistry http://dx.doi.org/10.1002/cber.19941271003 <jats:p><jats:bold>Highervalent Derivatives of the d‐Metal Acids, 14<jats:sup>[1]</jats:sup>. — Diimido Complexes [M(NR)<jats:sub>2</jats:sub>(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>(L)] of Tetravalent Molybedenum and Tungsten: Structure, Molecular Dynamics, and Activation of π‐Acidic Ligands</jats:bold></jats:p><jats:p>[M(NMes)<jats:sup>2</jats:sup>Cl<jats:sup>2</jats:sup>(dme)] (M = Mo <jats:bold>1</jats:bold>, W <jats:bold>2</jats:bold>; Mes = mesityl) or the <jats:italic>trans</jats:italic>‐phosphane complexes [M(NMes)<jats:sub>2</jats:sub>(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub>] (<jats:bold>3, 4</jats:bold>) are reduced by C<jats:sub>8</jats:sub>K in the presence of PMe<jats:sub>3</jats:sub> to give diamagnetic d<jats:sup>2</jats:sup> complexes [Mo(NMes)<jats:sup>2</jats:sup>(PMe<jats:sup>3</jats:sup>}<jats:sup>3</jats:sup>] (<jats:bold>5</jats:bold>) and [W(NMes)<jats:sub>2</jats:sub>‐(PMe<jats:sub>3</jats:sub>)<jats:sub>3</jats:sub>] (<jats:bold>6</jats:bold>). At least one PMe<jats:sub>3</jats:sub> ligand in <jats:bold>5</jats:bold> and <jats:bold>6</jats:bold> is readily substituted by more π‐acidic substrates such as ethene, ethyne, 2‐butyne, and P(OEt)<jats:sub>3</jats:sub>. The reaction with ethene leads to [Mo(NMes)<jats:sub>2</jats:sub>(η<jats:sup>2</jats:sup>‐C<jats:sub>2</jats:sub>H<jats:sub>4</jats:sub>)(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>7</jats:bold>) and [W(NMes)<jats:sub>2</jats:sub>‐(η<jats:sup>2</jats:sup>‐C<jats:sub>2</jats:sub>H<jats:sub>4</jats:sub>)(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>8</jats:bold>). Furthermore, pentacoordinate complexes [Mo(NMes)<jats:sub>2</jats:sub>(η<jats:sub>2</jats:sub>‐C<jats:sub>2</jats:sub>Me<jats:sub>2</jats:sub>)(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>9</jats:bold>), [W(NMes)<jats:sub>2</jats:sub>(η<jats:sup>2</jats:sup>‐C<jats:sub>2</jats:sub>H<jats:sub>2</jats:sub>)(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>10</jats:bold>), and [W(NMes)<jats:sub>2</jats:sub>(PMe<jats:sub>3</jats:sub>){P(OEt)<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>11</jats:bold>) have been synthesized from <jats:bold>5</jats:bold> or <jats:bold>6</jats:bold>. The X‐ray structure analysis of <jats:bold>8</jats:bold> reveals a trigonal‐bipyramidal geometry about tungsten with both arylimido groups perfectly lying in the equatorial mirror plane. The ethene ligand is occupying the third equatorial position. The C<jats:sub>2</jats:sub> vector is oriented perpendicular to the WN<jats:sub>2</jats:sub> plane. Dynamic NMR studies are consistent with a <jats:italic>tbp</jats:italic> geometry being also present in solution at the low‐temperature limit. At higher temperatures a rapid exchange of the PMe<jats:sub>3</jats:sub> ligands with noncoordinated phosphane according to a dissociative mechanism is observed.</jats:p> Diimidokomplexe [M(NR)<sub>2</sub>(PMe<sub>3</sub>)2(L)] des vierwertigen Molybdäns und Wolframs: Struktur, Moleküldynamik und Aktivierung π‐acider Liganden Chemische Berichte |
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10.1002/cber.19941271003 |
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Online |
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Chemie und Pharmazie |
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ElectronicArticle |
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Wiley, 1994 |
| imprint_str_mv |
Wiley, 1994 |
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English |
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1994 |
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Wiley |
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Chemische Berichte |
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49 |
| title |
Diimidokomplexe [M(NR)2(PMe3)2(L)] des vierwertigen Molybdäns und Wolframs: Struktur, Moleküldynamik und Aktivierung π‐acider Liganden |
| title_unstemmed |
Diimidokomplexe [M(NR)2(PMe3)2(L)] des vierwertigen Molybdäns und Wolframs: Struktur, Moleküldynamik und Aktivierung π‐acider Liganden |
| title_full |
Diimidokomplexe [M(NR)2(PMe3)2(L)] des vierwertigen Molybdäns und Wolframs: Struktur, Moleküldynamik und Aktivierung π‐acider Liganden |
| title_fullStr |
Diimidokomplexe [M(NR)2(PMe3)2(L)] des vierwertigen Molybdäns und Wolframs: Struktur, Moleküldynamik und Aktivierung π‐acider Liganden |
| title_full_unstemmed |
Diimidokomplexe [M(NR)2(PMe3)2(L)] des vierwertigen Molybdäns und Wolframs: Struktur, Moleküldynamik und Aktivierung π‐acider Liganden |
| title_short |
Diimidokomplexe [M(NR)2(PMe3)2(L)] des vierwertigen Molybdäns und Wolframs: Struktur, Moleküldynamik und Aktivierung π‐acider Liganden |
| title_sort |
diimidokomplexe [m(nr)<sub>2</sub>(pme<sub>3</sub>)2(l)] des vierwertigen molybdäns und wolframs: struktur, moleküldynamik und aktivierung π‐acider liganden |
| topic |
Inorganic Chemistry |
| url |
http://dx.doi.org/10.1002/cber.19941271003 |
| publishDate |
1994 |
| physical |
1827-1835 |
| description |
<jats:p><jats:bold>Highervalent Derivatives of the d‐Metal Acids, 14<jats:sup>[1]</jats:sup>. — Diimido Complexes [M(NR)<jats:sub>2</jats:sub>(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>(L)] of Tetravalent Molybedenum and Tungsten: Structure, Molecular Dynamics, and Activation of π‐Acidic Ligands</jats:bold></jats:p><jats:p>[M(NMes)<jats:sup>2</jats:sup>Cl<jats:sup>2</jats:sup>(dme)] (M = Mo <jats:bold>1</jats:bold>, W <jats:bold>2</jats:bold>; Mes = mesityl) or the <jats:italic>trans</jats:italic>‐phosphane complexes [M(NMes)<jats:sub>2</jats:sub>(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub>] (<jats:bold>3, 4</jats:bold>) are reduced by C<jats:sub>8</jats:sub>K in the presence of PMe<jats:sub>3</jats:sub> to give diamagnetic d<jats:sup>2</jats:sup> complexes [Mo(NMes)<jats:sup>2</jats:sup>(PMe<jats:sup>3</jats:sup>}<jats:sup>3</jats:sup>] (<jats:bold>5</jats:bold>) and [W(NMes)<jats:sub>2</jats:sub>‐(PMe<jats:sub>3</jats:sub>)<jats:sub>3</jats:sub>] (<jats:bold>6</jats:bold>). At least one PMe<jats:sub>3</jats:sub> ligand in <jats:bold>5</jats:bold> and <jats:bold>6</jats:bold> is readily substituted by more π‐acidic substrates such as ethene, ethyne, 2‐butyne, and P(OEt)<jats:sub>3</jats:sub>. The reaction with ethene leads to [Mo(NMes)<jats:sub>2</jats:sub>(η<jats:sup>2</jats:sup>‐C<jats:sub>2</jats:sub>H<jats:sub>4</jats:sub>)(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>7</jats:bold>) and [W(NMes)<jats:sub>2</jats:sub>‐(η<jats:sup>2</jats:sup>‐C<jats:sub>2</jats:sub>H<jats:sub>4</jats:sub>)(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>8</jats:bold>). Furthermore, pentacoordinate complexes [Mo(NMes)<jats:sub>2</jats:sub>(η<jats:sub>2</jats:sub>‐C<jats:sub>2</jats:sub>Me<jats:sub>2</jats:sub>)(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>9</jats:bold>), [W(NMes)<jats:sub>2</jats:sub>(η<jats:sup>2</jats:sup>‐C<jats:sub>2</jats:sub>H<jats:sub>2</jats:sub>)(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>10</jats:bold>), and [W(NMes)<jats:sub>2</jats:sub>(PMe<jats:sub>3</jats:sub>){P(OEt)<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>11</jats:bold>) have been synthesized from <jats:bold>5</jats:bold> or <jats:bold>6</jats:bold>. The X‐ray structure analysis of <jats:bold>8</jats:bold> reveals a trigonal‐bipyramidal geometry about tungsten with both arylimido groups perfectly lying in the equatorial mirror plane. The ethene ligand is occupying the third equatorial position. The C<jats:sub>2</jats:sub> vector is oriented perpendicular to the WN<jats:sub>2</jats:sub> plane. Dynamic NMR studies are consistent with a <jats:italic>tbp</jats:italic> geometry being also present in solution at the low‐temperature limit. At higher temperatures a rapid exchange of the PMe<jats:sub>3</jats:sub> ligands with noncoordinated phosphane according to a dissociative mechanism is observed.</jats:p> |
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| author | Radius, Udo, Sundermeyer, Jörg, Pritzkow, Hans |
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| container_issue | 10 |
| container_start_page | 1827 |
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| description | <jats:p><jats:bold>Highervalent Derivatives of the d‐Metal Acids, 14<jats:sup>[1]</jats:sup>. — Diimido Complexes [M(NR)<jats:sub>2</jats:sub>(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>(L)] of Tetravalent Molybedenum and Tungsten: Structure, Molecular Dynamics, and Activation of π‐Acidic Ligands</jats:bold></jats:p><jats:p>[M(NMes)<jats:sup>2</jats:sup>Cl<jats:sup>2</jats:sup>(dme)] (M = Mo <jats:bold>1</jats:bold>, W <jats:bold>2</jats:bold>; Mes = mesityl) or the <jats:italic>trans</jats:italic>‐phosphane complexes [M(NMes)<jats:sub>2</jats:sub>(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub>] (<jats:bold>3, 4</jats:bold>) are reduced by C<jats:sub>8</jats:sub>K in the presence of PMe<jats:sub>3</jats:sub> to give diamagnetic d<jats:sup>2</jats:sup> complexes [Mo(NMes)<jats:sup>2</jats:sup>(PMe<jats:sup>3</jats:sup>}<jats:sup>3</jats:sup>] (<jats:bold>5</jats:bold>) and [W(NMes)<jats:sub>2</jats:sub>‐(PMe<jats:sub>3</jats:sub>)<jats:sub>3</jats:sub>] (<jats:bold>6</jats:bold>). At least one PMe<jats:sub>3</jats:sub> ligand in <jats:bold>5</jats:bold> and <jats:bold>6</jats:bold> is readily substituted by more π‐acidic substrates such as ethene, ethyne, 2‐butyne, and P(OEt)<jats:sub>3</jats:sub>. The reaction with ethene leads to [Mo(NMes)<jats:sub>2</jats:sub>(η<jats:sup>2</jats:sup>‐C<jats:sub>2</jats:sub>H<jats:sub>4</jats:sub>)(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>7</jats:bold>) and [W(NMes)<jats:sub>2</jats:sub>‐(η<jats:sup>2</jats:sup>‐C<jats:sub>2</jats:sub>H<jats:sub>4</jats:sub>)(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>8</jats:bold>). Furthermore, pentacoordinate complexes [Mo(NMes)<jats:sub>2</jats:sub>(η<jats:sub>2</jats:sub>‐C<jats:sub>2</jats:sub>Me<jats:sub>2</jats:sub>)(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>9</jats:bold>), [W(NMes)<jats:sub>2</jats:sub>(η<jats:sup>2</jats:sup>‐C<jats:sub>2</jats:sub>H<jats:sub>2</jats:sub>)(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>10</jats:bold>), and [W(NMes)<jats:sub>2</jats:sub>(PMe<jats:sub>3</jats:sub>){P(OEt)<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>11</jats:bold>) have been synthesized from <jats:bold>5</jats:bold> or <jats:bold>6</jats:bold>. The X‐ray structure analysis of <jats:bold>8</jats:bold> reveals a trigonal‐bipyramidal geometry about tungsten with both arylimido groups perfectly lying in the equatorial mirror plane. The ethene ligand is occupying the third equatorial position. The C<jats:sub>2</jats:sub> vector is oriented perpendicular to the WN<jats:sub>2</jats:sub> plane. Dynamic NMR studies are consistent with a <jats:italic>tbp</jats:italic> geometry being also present in solution at the low‐temperature limit. At higher temperatures a rapid exchange of the PMe<jats:sub>3</jats:sub> ligands with noncoordinated phosphane according to a dissociative mechanism is observed.</jats:p> |
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| imprint | Wiley, 1994 |
| imprint_str_mv | Wiley, 1994 |
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| series | Chemische Berichte |
| source_id | 49 |
| spelling | Radius, Udo Sundermeyer, Jörg Pritzkow, Hans 0009-2940 Wiley Inorganic Chemistry http://dx.doi.org/10.1002/cber.19941271003 <jats:p><jats:bold>Highervalent Derivatives of the d‐Metal Acids, 14<jats:sup>[1]</jats:sup>. — Diimido Complexes [M(NR)<jats:sub>2</jats:sub>(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>(L)] of Tetravalent Molybedenum and Tungsten: Structure, Molecular Dynamics, and Activation of π‐Acidic Ligands</jats:bold></jats:p><jats:p>[M(NMes)<jats:sup>2</jats:sup>Cl<jats:sup>2</jats:sup>(dme)] (M = Mo <jats:bold>1</jats:bold>, W <jats:bold>2</jats:bold>; Mes = mesityl) or the <jats:italic>trans</jats:italic>‐phosphane complexes [M(NMes)<jats:sub>2</jats:sub>(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>Cl<jats:sub>2</jats:sub>] (<jats:bold>3, 4</jats:bold>) are reduced by C<jats:sub>8</jats:sub>K in the presence of PMe<jats:sub>3</jats:sub> to give diamagnetic d<jats:sup>2</jats:sup> complexes [Mo(NMes)<jats:sup>2</jats:sup>(PMe<jats:sup>3</jats:sup>}<jats:sup>3</jats:sup>] (<jats:bold>5</jats:bold>) and [W(NMes)<jats:sub>2</jats:sub>‐(PMe<jats:sub>3</jats:sub>)<jats:sub>3</jats:sub>] (<jats:bold>6</jats:bold>). At least one PMe<jats:sub>3</jats:sub> ligand in <jats:bold>5</jats:bold> and <jats:bold>6</jats:bold> is readily substituted by more π‐acidic substrates such as ethene, ethyne, 2‐butyne, and P(OEt)<jats:sub>3</jats:sub>. The reaction with ethene leads to [Mo(NMes)<jats:sub>2</jats:sub>(η<jats:sup>2</jats:sup>‐C<jats:sub>2</jats:sub>H<jats:sub>4</jats:sub>)(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>7</jats:bold>) and [W(NMes)<jats:sub>2</jats:sub>‐(η<jats:sup>2</jats:sup>‐C<jats:sub>2</jats:sub>H<jats:sub>4</jats:sub>)(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>8</jats:bold>). Furthermore, pentacoordinate complexes [Mo(NMes)<jats:sub>2</jats:sub>(η<jats:sub>2</jats:sub>‐C<jats:sub>2</jats:sub>Me<jats:sub>2</jats:sub>)(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>9</jats:bold>), [W(NMes)<jats:sub>2</jats:sub>(η<jats:sup>2</jats:sup>‐C<jats:sub>2</jats:sub>H<jats:sub>2</jats:sub>)(PMe<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>10</jats:bold>), and [W(NMes)<jats:sub>2</jats:sub>(PMe<jats:sub>3</jats:sub>){P(OEt)<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>11</jats:bold>) have been synthesized from <jats:bold>5</jats:bold> or <jats:bold>6</jats:bold>. The X‐ray structure analysis of <jats:bold>8</jats:bold> reveals a trigonal‐bipyramidal geometry about tungsten with both arylimido groups perfectly lying in the equatorial mirror plane. The ethene ligand is occupying the third equatorial position. The C<jats:sub>2</jats:sub> vector is oriented perpendicular to the WN<jats:sub>2</jats:sub> plane. Dynamic NMR studies are consistent with a <jats:italic>tbp</jats:italic> geometry being also present in solution at the low‐temperature limit. At higher temperatures a rapid exchange of the PMe<jats:sub>3</jats:sub> ligands with noncoordinated phosphane according to a dissociative mechanism is observed.</jats:p> Diimidokomplexe [M(NR)<sub>2</sub>(PMe<sub>3</sub>)2(L)] des vierwertigen Molybdäns und Wolframs: Struktur, Moleküldynamik und Aktivierung π‐acider Liganden Chemische Berichte |
| spellingShingle | Radius, Udo, Sundermeyer, Jörg, Pritzkow, Hans, Chemische Berichte, Diimidokomplexe [M(NR)2(PMe3)2(L)] des vierwertigen Molybdäns und Wolframs: Struktur, Moleküldynamik und Aktivierung π‐acider Liganden, Inorganic Chemistry |
| title | Diimidokomplexe [M(NR)2(PMe3)2(L)] des vierwertigen Molybdäns und Wolframs: Struktur, Moleküldynamik und Aktivierung π‐acider Liganden |
| title_full | Diimidokomplexe [M(NR)2(PMe3)2(L)] des vierwertigen Molybdäns und Wolframs: Struktur, Moleküldynamik und Aktivierung π‐acider Liganden |
| title_fullStr | Diimidokomplexe [M(NR)2(PMe3)2(L)] des vierwertigen Molybdäns und Wolframs: Struktur, Moleküldynamik und Aktivierung π‐acider Liganden |
| title_full_unstemmed | Diimidokomplexe [M(NR)2(PMe3)2(L)] des vierwertigen Molybdäns und Wolframs: Struktur, Moleküldynamik und Aktivierung π‐acider Liganden |
| title_short | Diimidokomplexe [M(NR)2(PMe3)2(L)] des vierwertigen Molybdäns und Wolframs: Struktur, Moleküldynamik und Aktivierung π‐acider Liganden |
| title_sort | diimidokomplexe [m(nr)<sub>2</sub>(pme<sub>3</sub>)2(l)] des vierwertigen molybdäns und wolframs: struktur, moleküldynamik und aktivierung π‐acider liganden |
| title_unstemmed | Diimidokomplexe [M(NR)2(PMe3)2(L)] des vierwertigen Molybdäns und Wolframs: Struktur, Moleküldynamik und Aktivierung π‐acider Liganden |
| topic | Inorganic Chemistry |
| url | http://dx.doi.org/10.1002/cber.19941271003 |