Cyclic voltammetry studies of two L(X)Ga-substituted dipnictenes [L(R2N)GaE]2 (E = Sb, R = Me 1; E =Bi; R = Et 2; L = HC[C(Me)NDipp]2; Dipp= 2,6-i-Pr2C6H3) showed reversible reduction events....
Stable heavy main group element radicals are challenging synthetic targets. Although several strategies have been developed to stabilize such odd-electron species, the number of heavier pnictogen-centered radicals is limited. We report on a series of two-coordinated pnictogen-centered radical cations [( Me cAAC)EGa(Cl)L][B(C 6 F 5 ) 4 ] ( Me cAAC = [H 2 C-(CMe 2 ) 2 NDipp]C; Dipp = 2,6-i-Pr 2 C 6 H 3 ; E = As 1, Sb 2, Bi 3; L = HC[C(Me)NDipp] 2 ) synthesized by one-electron oxidation of L(Cl)Ga-substituted pnictinidenes ( Me cAAC)EGa(Cl)L (E = As I, Sb II, Bi III). 1−3 were characterized by electron paramagnetic resonance (EPR) spectroscopy and single crystal X-ray diffraction (sc-XRD) (1, 2), while quantum chemical calculations support their description as carbene-coordinated pnictogen-centered radical cations. The low thermal stability of 3 enables access to metalloid bismuth clusters as shown by formation of [{LGa(Cl)} 3 Bi 6 ][B(C 6 F 5 ) 4 ] (4).
The bis(thiophosphinite) pincer complexes [(RPSCSPR)Rh(py)(H)(Cl)] (RPSCSPR = C6H4-2,6-(SPR2)2 with R = iPr, 2a and R = Ph, 2a) are prepared by metalation of the ligand precursor with [Rh(cod)Cl]2 in the...
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