Conversion of trans‐Diboran(4)yl Platinum Complexes into Their cis‐Bisboryl Analogues. Issue 43 (11th September 2013)

• Record Type: Journal Article
• Authors: Braunschweig, Holger; Damme, Alexander; Kupfer, Thomas
• Is Part Of: Chemistry. Volume 19:Issue 43(2013)
• Page Start: 14682
• Page End: 14686
• Publication Date: 2013-09-11
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201301827
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>The diboran(4)yl <italic>trans</italic>‐[(<italic>i</italic>Pr₃P)₂Pt(Br){B(NMe₂)B(NMe₂)Br}] (<bold>1</bold>) is readily converted into its <italic>cis</italic>‐bisboryl analogues <bold>2</bold> and <bold>3</bold> by reaction with the chelating bisphosphines 1, 2‐bis(dicyclohexylphosphino)ethane (dcpe) and 1, 1‐bis(dicyclohexylphosphino)methane (dcpm), respectively. A plausible mechanism of this transformation consists of a sequence of reductive diborane(4) elimination and subsequent reoxidative addition of its BB bond to the low‐valent platinum centers. Thus, the forced <italic>cis</italic> configuration of the phosphine ligands induces a change in the preferred reaction site of the diborane(4) with respect to oxidative addition. The reactions proceed with high selectivities, and the <italic>cis</italic>‐bisboryl complexes <bold>2</bold> and <bold>3</bold> were isolated in moderate yields (55 and 46 %). Moreover, their identity was clearly verified by NMR spectroscopy and X‐ray diffraction studies.</p> </abstract>