4.6 Article

Nitric Oxide Insertion Reactivity with the Bismuth-Carbon Bond: Formation of the Oximate Anion, [ON=(C6H2tBu2O)]-, from the Oxyaryl Dianion, (C6H2tBu2O)2-

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CHEMISTRY-A EUROPEAN JOURNAL
卷 20, 期 46, 页码 15242-15247

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WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201404910

关键词

bismuth; nitric oxide; oximates; oxyaryl dianion; synthetic methods

资金

  1. Chemical Science, Geosciences, and Biosciences Division of the Office of Basic Energy Sciences of the Department of Energy [DE-SC0004739]
  2. U.S. Department of Energy (DOE) [DE-SC0004739] Funding Source: U.S. Department of Energy (DOE)

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The first example of NO insertion into a BiC bond has been found in the direct reaction of NO with a Bi3+ complex of the unusual (C(6)H(2)tBu(2)-3,5-O-4)(2-) oxyaryl dianionic ligand, namely, ArBi(C(6)H(2)tBu(2)-3,5-O-4) [Ar=2,6-(Me2NCH2)(2)C6H3] (1). The oximate complexes [ArBi(ONC6H2-3,5-tBu(2)-4-O)](2)(-O) (3) and ArBi(ONC6H2-3,5-tBu(2)-4-O)(2) (4) were formed as a mixture, but can be isolated in pure form by reaction of NO with a Bi3+ complex of the [O2C(C(6)H(2)tBu(2)-3-5-O-4](2-) oxyarylcarboxy dianion, namely, ArBi[O2C(C(6)H(2)tBu(2)-3-5-O-4)-O-2,O']. Reaction of 1 with Ph3CSNO gave an oximate product with (Ph3CS)(1-) as an ancillary ligand, (Ph3CS)(Ar)Bi(ONC6H2-3,5-tBu(2)-4-O) (5).

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