The transmetalation reaction of picolyl-supported tridentate nacnac germylene monochloride [2,6-iPr2–C6H3NC(Me)CHC(Me)NH(CH2py)]GeCl (1) (py = pyridine) with SnCl2 results in an analogous stannylene chloride (2). The three-coordinated stannylenium cation [{2,6-iPr2–C6H3NC(Me)CHC(Me)NH(CH2py)}Sn]+ with SnCl3 – as a counteranion (3) has been generated through the abstraction of chloride ligand from 2 using an additional equivalent of SnCl2. Instead of forming a donor–acceptor complex, 2 undergoes a facile redox transmetalation reaction with Ni(COD)2 (COD = cyclooctadiene) and CuCl to afford analogous nickel and copper complexes [2,6-iPr2–C6H3NC(Me)CHC(Me)NH(CH2py)]MCl [M = Ni (4) and Cu (5)]. The reactions of 4 with potassium tri-sec-butylborohydride (commonly known as K-selectride) and AgSbF6 provide access to monomeric Ni(II) hydride, [2,6-iPr2–C6H3NC(Me)CHC(Me)NH(CH2py)]NiH (6) and a Ni(II) cation, [{2,6-iPr2–C6H3NC(Me)CHC(Me)NH(CH2py)}Ni][SbF6] (7), respectively. 6 was found to be an effective catalyst for the hydroboration of amides.

Described herein an alternative synthetic approach for conjugated indeno[2,1-c]fluorene, including the experimental and theoretical investigations of a tetraradicaloid s-indaceno[2,1-c:6,5-c']difluorene that belongs to the rarely explored indacenodifluorene family containing 4n+2 monocyclic...

Described herein are the steric promoted synthesis and characterization of symmetric, unsymmetric, and benzo-extended indeno[1,2-b]fluorenes 1-5, including isolation of a stable 4nπ indeno[2,1-a]fluorene 6. Single-crystal XRD analyses of 5 and...

Dicyclopenta[c]fluorenothiophene 5 was synthesized as the isoelectronic polycyclic heteroarene analogue of an as-indacenodifluorene with a (4n + 2)π-electron perimeter. Single-crystal and 1 H NMR analyses indicated a quinoidal ground state for 5, which was supported by theoretical calculations while suggesting a degree of antiaromaticity of the as-indacene subunit greater than that for sindacenodifluorene 3. The dominant antiaromaticity for 5 was evidenced by the broad weakly intense absorption tail reaching the near-IR region, four-stage redox amphotericity, and small HOMO− LUMO energy gap.