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Monohaloboryls (BHX − ) as Bridging Ligands: Observable Dinuclear σ‐(Halo)boranyl Intermediates in the Synthesis of Metalloborylenes
Author(s) -
Bauer Jürgen,
Braunschweig Holger,
Dewhurst Rian D.,
Kraft Katharina,
Radacki Krzysztof
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201103163
Subject(s) - chemistry , halo , metal , crystallography , hydride , boron , stereochemistry , ligand (biochemistry) , physics , organic chemistry , biochemistry , receptor , quantum mechanics , galaxy
Upon treating transition‐metal–dihaloboryl complexes of the form [L n MBX 2 ] with K[(η 5 ‐C 5 H 5 )MnH(CO) 2 ], salt elimination occurs along with a migration of the Mn‐bound hydride ligand onto the boron atom, thereby forming dinuclear σ‐(halo)boranyl complexes of the form [L n M(μ ‐ BHX)Mn(CO) 2 (η 5 ‐C 5 H 5 )]. Most of these complexes react further at room temperature to lose HX and provide metalloborylene complexes [L n M‐B=Mn(CO) 2 (η 5 ‐C 5 H 5 )]; however, when ML n =Re(CO) 5 the σ‐(halo)boranyl complex decomposes into unidentifiable products. We found through DFT calculations that two electronically and structurally distinct forms of the intermediate σ‐(halo)boranyl complexes exist, one of which easily loses HX and one that does not.