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Multi-Talented Bismuthinidenes: Double C(sp3)─I Bond Activation Using Single or Two Bi Centers
Pavel Novák1, Martin Hejda1, Roman Jambor1
1Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, Studentská 573, Pardubice, CZ-532 10, Czech Republic.
Abstract:
The reaction of [2,6-(DippN = CH)2C6H3]Bi (1Dipp, Dipp = 2,6-iPrC6H3) with CH2I2 proceeded via double C─I bond activation yielding [2,6-(DippN = CH)2C6H3]Bi(μ-(Bi,N)─CH2)I2 (3). By contrast, the reaction of 1Dipp with 1,2-diiodoethane provided [2,6-(DippN═CH)2C6H3]BiI2 (1DippI2) and ethene. The tert-butyl analogue [2,6-(tBuN═CH)2C6H3]Bi (1tBu) reacted with CH2ClX to give [2,6-(tBuN═CH)2C6H3]Bi(CH2Cl)X (X═I (4) or Cl (5)). Further, its reactivity with CH2I2 was sensitive towards the stoichiometry since using a 1:1 ratio gave a mixture of dinuclear complex {[2,6-(tBuN═CH)2C6H3]Bi(I)}2(μ-(Bi,Bi)─CH2) (6) and [2,6-(tBuN═CH)2C6H3]Bi(CH2I)I (7). The reaction could be shifted in favor of 7 using an excess of CH2I2, but with 0.45 eq. of CH2I2 compound 6, as a product of double C─I bond activation mediated by two Bi atoms was isolated as the main product.
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