Reductive activation of tripod metal compounds:: Identification of intermediates and preparative application

Publikationstyp:
Zeitschriftenaufsatz
Metadaten:
Autoren
  • Juergen Mautz
  • Katja Heinze
  • Hubert Wadepohl
  • Gottfried Huttner
Autoren-URL
https://www.webofscience.com/api/gateway?GWVersion=2&SrcApp=fis-test-1&SrcAuth=WosAPI&KeyUT=WOS:000254555300008&DestLinkType=FullRecord&DestApp=WOS_CPL
DOI
10.1002/ejic.200700873
Externe Identifier
  • Clarivate Analytics Document Solution ID: 282GI
ISSN
1434-1948
Ausgabe der Veröffentlichung
9
Zeitschrift
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
Schlüsselwörter
  • tripodal ligands
  • cobalt
  • nickel
  • reductive activation
  • oxidative addition
  • silicon hydrides
  • tin hydrides
Paginierung
1413 - 1422
Datum der Veröffentlichung
2008
Status
Published
Titel
Reductive activation of <i>tripod</i> metal compounds:: Identification of intermediates and preparative application
Sub types
  • Article

Datenquelle: Web of Science (Lite)

Andere Metadatenquellen:
Abstract
<jats:title>Abstract</jats:title><jats:p>[<jats:italic>tripod</jats:italic>CoCl<jats:sub>2</jats:sub>] {<jats:italic>tripod</jats:italic> = CH<jats:sub>3</jats:sub>C(CH<jats:sub>2</jats:sub>PPh<jats:sub>2</jats:sub>)<jats:sub>3</jats:sub>} when treated with KC<jats:sub>8</jats:sub> in THF solution under an argon atmosphere produces a reactive species [“<jats:italic>tripod</jats:italic>Co<jats:sup>0</jats:sup>”] (<jats:bold>A</jats:bold>) which undergoes oxidative additions with stannanes, [<jats:italic>tripod</jats:italic>Co(H)<jats:sub>2</jats:sub>(SnBu<jats:sub>3</jats:sub>)] (<jats:bold>4</jats:bold>), formed, for example, by addition of Bu<jats:sub>3</jats:sub>SnH. Silanes, R<jats:sub>3</jats:sub>SiH, undergo the same type of reaction producing [<jats:italic>tripod</jats:italic>Co(H)<jats:sub>2</jats:sub>(SiR<jats:sub>3</jats:sub>)] (R = Et: <jats:bold>5a</jats:bold>; R = Ph: <jats:bold>5b</jats:bold>). The solid‐state structures of all the compounds [<jats:italic>tripod</jats:italic>Co(H)<jats:sub>2</jats:sub>(ER<jats:sub>3</jats:sub>)] (E = Si, R = Ph; E = Sn, R = Ph, Bu) are rather similar. While they contain six‐coordinate cobalt with the formal oxidation state of cobalt being +III the coordination geometry is not octahedral: the heteroelement E deviates from the position which it would have in octahedral coordination by around 40° while the other five ligands, three phosphorus and two hydrogen, have the expected interligand angles of around 90° and 180°, respectively. The deviation of the heteroelement E is such that it approaches the metal bonded hydrogen atoms leading to short H<jats:bold>···</jats:bold>E contacts of only about 190 pm (E = Si) and 230 pm (E = Sn), respectively. The generation of a reactive species [“<jats:italic>tripod</jats:italic>Co<jats:sup>0</jats:sup>”] (<jats:bold>A</jats:bold>) was transferred to the synthesis of a reactive <jats:italic>tripod</jats:italic>nickel(0) species by treating a THF solution of [(DME)NiBr<jats:sub>2</jats:sub>] with KC<jats:sub>8</jats:sub> in the presence of <jats:italic>tripod</jats:italic>. This species reacts with two electron donor ligands L to produce the pseudo tetrahedral compounds [<jats:italic>tripod</jats:italic>Ni(L)] {L = PPh<jats:sub>3</jats:sub> (<jats:bold>6</jats:bold>), AsPh<jats:sub>3</jats:sub> (<jats:bold>7</jats:bold>), cHexNC (<jats:bold>8</jats:bold>), <jats:italic>t</jats:italic>BuNC (<jats:bold>9</jats:bold>), C<jats:sub>2</jats:sub>H<jats:sub>4</jats:sub> (<jats:bold>10</jats:bold>)}. The identity of the reactive nickel(0) species as unequivocally deduced from NMR experiments is [<jats:italic>tripod</jats:italic><jats:sub>4</jats:sub>Ni<jats:sub>3</jats:sub>] (<jats:bold>12</jats:bold>). All compounds were characterised by the usual analytic techniques including X‐ray analysis where applicable.(© Wiley‐VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2008)</jats:p>
Autoren
  • Jürgen Mautz
  • Katja Heinze
  • Hubert Wadepohl
  • Gottfried Huttner
DOI
10.1002/ejic.200700873
eISSN
1099-0682
ISSN
1434-1948
Ausgabe der Veröffentlichung
9
Zeitschrift
European Journal of Inorganic Chemistry
Sprache
en
Online publication date
2008
Paginierung
1413 - 1422
Datum der Veröffentlichung
2008
Status
Published
Herausgeber
Wiley
Herausgeber URL
http://dx.doi.org/10.1002/ejic.200700873
Datum der Datenerfassung
2023
Titel
Reductive Activation of <i>tripod</i> Metal Compounds: Identification of Intermediates and Preparative Application
Ausgabe der Zeitschrift
2008

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