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Zeitschrift für Naturforschung B

A Journal of Chemical Sciences


IMPACT FACTOR 2018: 0.961

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1865-7117
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Volume 73, Issue 11

Issues

Functionalization of 1,3-diphosphacyclobutadiene cobalt complexes via Si–P bond insertion

Christian Rödl
  • Institut für Anorganische Chemie, Universität Regensburg, Universitätsstraße 31, 93053 Regensburg, Germany
  • Other articles by this author:
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/ Jennifer Bissmeyer neé Malberg
  • Institut für Anorganische Chemie, Universität Regensburg, Universitätsstraße 31, 93053 Regensburg, Germany
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Robert Wolf
  • Corresponding author
  • Institut für Anorganische Chemie, Universität Regensburg, Universitätsstraße 31, 93053 Regensburg, Germany
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  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
Published Online: 2018-10-18 | DOI: https://doi.org/10.1515/znb-2018-0121

Abstract

We report the synthesis of functionalized 1,3-bis(diphosphacyclobutadiene) complexes via the insertion of carbon-oxygen bonds of ethers, esters, aldehydes and amides into the P–Si bond of silylated complexes. Reactions of [K(tol)2][Co(η4-P2C2R2)2] [[K(tol)2][1a]: R=tBu, [K(tol)2][1b]: R=tPent (=tert-pentyl)] with Me3SiCl afford the trimethylsilyl-substituted derivatives [Co(η4-P2C2R2SiMe3)(η4-P2C2R2)] (2a,b, R=tBu, tPent). The Me3Si group is connected to a phosphorus atom of one of the 1,3-diphosphacyclobutadiene ligands. 2a,b readily react with organic substrates containing C–O single and C=O double bonds at ambient temperature. [Co(η4-P2C2R2(CH2)4OSiMe3)(η4-P2C2R2)] (3a, b) are formed by reaction of 2a, b with traces of THF. They can also be isolated by reacting the THF solvates [K(thf)2{Co(P2C2tBu2)2}] ([K(thf)2][1a]) and [K(thf)3{Co(P2C2tPent2)2}] ([K(thf)3][1b]) with Me3SiCl in toluene or THF. The adamantyl-substituted complex [Co(η4-P2C2Ad2(CH2)4OSiMe3)(η4-P2C2Ad2)] (3c) was prepared analogously from [K(thf)4{Co(P2C2Ad2)2}] and Me3SiCl. [K(thf)2][1a] reacts cleanly with Ph3SnCl affording [Co(η4-P2C2tBu2SnPh3)(η4-P2C2tBu2)] (4) in high yield. Reaction of 2a with styrene oxide affords [Co(η4-P2C2tBu2PhC2H3OSiMe3)(η4-P2C2tBu2)] (5) as a single regioisomer. By contrast, multinuclear NMR spectroscopic studies indicate mixtures of two isomeric insertion products 6/6′ and 7/7′, respectively, which result from the insertion of 1,2-epoxy-2-methylpropane and 1,2-epoxyoctane. Moreover, these monitoring studies show that reactions of 2a with acyclic ethers afford alkyl substituted complexes such as [Co(η4-P2C2tBu2Et)(η4-P2C2tBu2)] (8) and alkylsilyl ethers. Reaction of 2a with γ-butyrolactone gives [Co(η4-P2C2tBu2(CH2)3C(O)OSiMe3)(η4-P2C2tBu2)] (9) via cleavage of the endocyclic C–O single bond of the lactone. Benzaldehyde and acetone cleanly react with 2a to [Co(η4-P2C2tBu2CH(Ph)OSiMe3)(η4-P2C2tBu2)] (10) and [Co(η4-P2C2tBu2CMe2OSiMe3)(η4-P2C2tBu2)] (11), while the sterically more demanding ketones 3-pentanone and acetophenone selectively yield the known hydride complex [Co(η4-P2C2tBu2)2H] (A). Phenyl isocyanate reacts with 2a at elevated temperature to form [Co(η3-P2C2tBu2CON(Ph)SiMe3)(η4-P2C2tBu2)] (12) with a functionalized η3-coordinated ligand. [K(tol)2][1a], [K(tol)2][1b], 2a, 2b, 3a–c, 4, 5, and 9–12 were isolated and characterized by multinuclear NMR spectroscopy, UV/Vis spectroscopy and elemental analysis. [K(tol)2][1b], 2a, 2b, 3c, 4, 5, and 9–12 were additionally characterized by X-ray crystallography.

This article offers supplementary material which is provided at the end of the article.

Keywords: cobalt; phosphorus; sandwich complexes; silicon

Dedicated to: Professor Werner Uhl on the occasion of his 65th birthday.

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About the article

Received: 2018-06-17

Accepted: 2018-08-14

Published Online: 2018-10-18

Published in Print: 2018-11-27


Citation Information: Zeitschrift für Naturforschung B, Volume 73, Issue 11, Pages 895–909, ISSN (Online) 1865-7117, ISSN (Print) 0932-0776, DOI: https://doi.org/10.1515/znb-2018-0121.

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