4.5 Article

Unexpected reactions of chromium hydrides with a diazoalkane

Journal

POLYHEDRON
Volume 157, Issue -, Pages 381-388

Publisher

PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.poly.2018.10.030

Keywords

Chromium; Hydride; Diazoalkane; Diketiminate ligand; Dinitrogen complex

Funding

  1. U.S. National Science Foundation [CHE-1565955]
  2. NSF [CHE-1048367, CHE-0840401]
  3. NIH [P20GM104316, P30GM110758, S10RR026962-01]

Ask authors/readers for more resources

The reaction of dinuclear chromium hydride [(2,6-Me2Ph)(2)nacnacCr(mu-H)](2) ((2,6-Me2Ph)(2)nacnac = N,N'-bis(2,6-dimethylphenyl)-2,4-pentanediiminato) with trimethylsilyl-diazomethane did not yield the desired, known alkyl hydride [(2,6-Me2Ph)(2)nacnacCr](2)(mu-H)(mu-CH2SiMe3). Rather, it resulted in an unexpected mixture of novel chromium complexes, which have been structurally characterized. They include macrocyclic dinitrogen complexes, namely [(2,6-Me2Ph)(2)nacnacCr(THF)(mu-N-2)](3) (4) and [(2,6-Me2Ph)(2)nacnacCr(mu-N-2)](4) (5). Other products containing various fragments of the diazo-reagent were [(2,6-Me2Ph)(2)nacnacCr](2)(mu-N)(mu-H) (6), [(2,6-Me2Ph)(2)nacnacCr](2)(mu-NSiMe3)(mu-H) (7) and [(2,6-Me2Ph)(2)nacnacCr](2)(mu-N=CH2)(mu-NH) (8). An analogous reaction of the sterically more encumbered [(2,6-iPr(2)Ph)(2)nacnacCr(mu-H)](2) ((2,6-Me2Ph)(2)nacnac = N,N'-bis(2,6-diisopropylphenyl)-2,4-pentanediimi-nato) produced [(2,6-iPr(2)Ph)(2)nacnacCr(mu-N)(mu-N(H)NC(H)SiMe3)](2) (9). (C) 2018 Elsevier Ltd. All rights reserved.

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