The doubly base-stabilized diborane(4) (HB(μ-hpp))2 (hpp = 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinate): synthesis by catalytic dehydrogenation and reactions with S8 and disulfides

In this work we report on new experiments on the catalytic dehydrogenation of [H2B(μ-hpp)]2 leading to the doubly base-stabilized diborane(4) [HB(μ-hpp)]2 featuring two hpp bridges (hpp = 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinate) under mild conditions. Several dehydrogenation (pre)cataly...

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Main Authors: Schulenberg, Nikola (Author) , Ciobanu, Oxana (Author) , Kaifer, Elisabeth (Author) , Wadepohl, Hubert (Author) , Himmel, Hans-Jörg (Author)
Format: Article (Journal)
Language:English
Published: August 24, 2010
In: European journal of inorganic chemistry
Year: 2010, Issue: 33, Pages: 5201-5210
ISSN:1099-0682
DOI:10.1002/ejic.201000637
Online Access:Resolving-System, lizenzpflichtig, Volltext: https://doi.org/10.1002/ejic.201000637
Verlag, lizenzpflichtig, Volltext: https://onlinelibrary.wiley.com/doi/abs/10.1002/ejic.201000637
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Author Notes:Nikola Schulenberg, Oxana Ciobanu, Elisabeth Kaifer, Hubert Wadepohl, and Hans-Jörg Himmel
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Summary:In this work we report on new experiments on the catalytic dehydrogenation of [H2B(μ-hpp)]2 leading to the doubly base-stabilized diborane(4) [HB(μ-hpp)]2 featuring two hpp bridges (hpp = 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinate) under mild conditions. Several dehydrogenation (pre)catalysts were tested. The best one turned out to be Ru3(CO)12, allowing quantitative dehydrogenation already at 60 °C. Subsequently we subjected [HB(μ-hpp)]2 to reactions with S8 and disulfides (Ph2S2 and Bn2S2, Bn = benzyl). Reaction with S8 leads to oxidative insertion of one sulfur atom into the B-B bond and formation of [HB(μ-hpp)]2(μ-S). In the case of disulfides, substitution reactions leading to the doubly base-stabilized diborane(4) species [RSB(μ-hpp)]2 and HB(μ-hpp)2BSR (R = Ph or Bn) compete with sulfuration again leading to [HB(μ-hpp)]2(μ-S).
Item Description:Im Titel erscheinen die Bezeichnungen "HB(μ-hpp)" und "1,2-a" in eckigen Klammern
Beim Ausdruck [HB(μ-hpp)]2 erscheint die Ziffer 2 tiefgestellt
Beim Ausdruck S8 erscheint die Ziffer 8 tiefgestellt
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Physical Description:Online Resource
ISSN:1099-0682
DOI:10.1002/ejic.201000637