Electron-Poor 2,3-Dihydro-1,3-diborolyl Ruthenium Compounds: Synthesis, Complexation, Oxidative Addition, Capping, and Stacking Reactions

✍ Scribed by Thomas Müller; Michael Kaschke; Melanie Strauch; Achim Ginsberg; Hans Pritzkow; Walter Siebert; Walter Siebert

• Publisher: John Wiley and Sons
• Year: 1999
• Tongue: English
• Weight: 418 KB
• Volume: 1999
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/(sici)1099-0682(199910)1999:10<1685::aid-ejic1685>3.0.co;2-#

✦ Synopsis

The addition products of lithium alkyls and the pentaalkyl-analyses. At low temperature the interaction of 2*a, c, or e with H 2 yields the classic dihydride complexes 7*a, c, and e, 2,3-dihydro-1,3-diborole derivatives 5a-f react with [{(C 5 Me 5 )RuCl} 4 ] and [{(C 5 Me 4 Et)RuCl} 4 ] to form the violet respectively, which have been studied by NMR. Oxidative addition of H 3 B•THF to the ruthenium atom of 2*a or c, sandwich compounds 2*c-f and 2 ∧ c, f. These formally 16 VE complexes are in fact electron-poor 18 VE species, because followed by a reductive elimination of H 2 and migration of the boranediyl group gives the yellow closo-RuC 3 B 3 a high-lying combination of σ(B-C) orbitals interacts with the d xz orbital of the Ru atom. Addition of tert-butyl isocyanide ruthenacarboranes 8*a and 8*c, respectively. The reaction of [(C 2 H 4 ) 2 RhCl] 2 and 2*c generates the tetranuclear complex to 2*a, or 2*d leads to the isonitrile complexes 6*a, and 6*d, as indicated by the spectroscopic data and X-ray structure 9*c.