Abstract
The synthesis and characterisation of a new anionic flexible scorpionate ligand, methyl(bis-7-azaindolyl)borohydride [MeBai]- is reported herein. The ligand was coordinated to a series of group nine transition metal centres forming the complexes, [Ir(MeBai)(COD)] (1), [Rh(MeBai)(COD)] (2), [Rh(MeBai)(CODMe)] (2-Me) and [Rh(MeBai)(NBD)] (3), where COD = 1,5-cyclooctadiene, CODMe = 3-methyl-1,5-cyclooctadiene and NBD = 2,5-norbornadiene. In all cases, the boron based ligand was found to bind to the metal centres via a κ3-N,N,H coordination mode. The ligand and complexes were fully characterised by spectroscopic and analytical methods. The structures of the ligand and three of the complexes were confirmed by X-ray crystallography. The potential for migration of the "hydride" or "methyl" units from boron to the metal centre was also explored. During these studies an unusual transformation, involving the oxidation of the rhodium centre, was observed in complex 2. In this case, the η4-COD unit transformed into a η1,η3-C8H12 unit where the ring was bound via one sigma bond and one allyl unit. This is the first time such a transformation has been observed at a rhodium centre.
References
Sep 5, 2001·Inorganic Chemistry·P J BaileyS Parsons
Feb 11, 2005·Dalton Transactions : an International Journal of Inorganic Chemistry·Helen R BigmoreCara S Tredget
Dec 22, 2005·Journal of the American Chemical Society·Marta MartínLuis A Oro
Jul 21, 2007·Angewandte Chemie·Eugene KhaskinAndrei N Vedernikov
Dec 25, 2007·Acta Crystallographica. Section A, Foundations of Crystallography·George M Sheldrick
Dec 17, 2008·Dalton Transactions : an International Journal of Inorganic Chemistry·Nikolaos TsoureasA Guy Orpen
Jan 28, 2009·Acta Crystallographica. Section D, Biological Crystallography·Anthony L Spek
Mar 20, 2010·Chemical Reviews·Holger BraunschweigAchim Schneider
Apr 29, 2010·Chemical Communications : Chem Comm·Romaeo DallanegraAndrew S Weller
May 8, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Gavin DysonGareth R Owen
Oct 13, 2010·Chemical Communications : Chem Comm·Nikolaos TsoureasGareth R Owen
Nov 26, 2010·Chemical Communications : Chem Comm·Abderrahmane Amgoune, Didier Bourissou
Dec 1, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Holger Braunschweig, Rian D Dewhurst
Dec 7, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Nikolaos TsoureasGareth R Owen
Jan 26, 2011·Chemical Communications : Chem Comm·Ahmed Al-HarbiGerard Parkin
Apr 30, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Gareth R OwenMairi F Haddow
May 5, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Keita YoshidaHiroshi Shinokubo
Oct 1, 2011·Chemical Communications : Chem Comm·Philip J BaileySimon Parsons
Nov 15, 2011·Chemical Communications : Chem Comm·Jing ZhuAaron D Sadow
Feb 15, 2012·Chemical Society Reviews·Gareth R Owen
May 24, 2012·Dalton Transactions : an International Journal of Inorganic Chemistry·Shrinwantu Pal, Andrei N Vedernikov
Sep 29, 2012·Topics in Current Chemistry·Abderrahmane AmgouneDidier Bourissou
Jun 6, 2013·Chemistry, an Asian Journal·Hajime Kameo, Hiroshi Nakazawa
Aug 27, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Silke FrömelGerhard Erker
Sep 6, 2013·Acta Crystallographica. Section C, Crystal Structure Communications·Glenn P A Yap
Dec 10, 2014·Angewandte Chemie·Marc DevillardDidier Bourissou
Dec 30, 2014·Acta Crystallographica. Section A, Foundations and Advances·George M Sheldrick
Jan 9, 2015·Acta Crystallographica. Section C, Structural Chemistry·George M Sheldrick
Nov 17, 2015·Chemical Society Reviews·Ghenwa Bouhadir, Didier Bourissou
Jan 30, 2016·Journal of the American Chemical Society·Wei-Chun ShihOleg V Ozerov
May 11, 2016·Chemical Reviews·Ayan Maity, Thomas S Teets
Aug 5, 2016·Chemical Communications : Chem Comm·Gareth R Owen
Apr 27, 2017·Chemistry : a European Journal·Koushik SahaSundargopal Ghosh