Synthesis and Fluorescence Studies of Diborene Coinage Metal Complexes.

Nine different coinage metal (Cu, Ag) π complexes of diborenes with various anionic diborene (aryl, heteroaryl) and metal substituents (Cl, Br, C6F5, C2SiMe3), stabilizing neutral donors (N-heterocyclic carbene = NHC, phosphine), configurations (cis/trans, acyclic/cyclic diborene), and charges (neutral, cationic) were synthesized and characterized by multinuclear NMR spectroscopy and X-ray crystallographic analyses. Their optical properties were investigated by UV-vis absorption and steady-state as well as time-resolved luminescence spectroscopy in solution and the solid state to gain insights into the excited-state behavior of this unusual class of photoactive compounds and to provide structure-property relationships. The structural and electronic modification of the (B═B)···M motif greatly influences not only the visible light absorption but also the photostability and quantum yields, which can reach high values of up to f = 0.42. The lifetimes are found in the nanosecond regime, providing estimated radiative rate constants over a wide range of kr = 1.3-14 × 107 s-1, indicative of fluorescence. Intersystem crossing (ISC) is sufficiently slow for prompt emission from the S1 state to be observed, while the spin-orbit coupling in the T1 state is too weak for phosphorescence to occur at room temperature. ISC can be accelerated, however, by modifying diborene ligand substitution and the coinage metal center, hinting at the potential for exploiting the properties of long-lived triplet excited states of metal diborene complexes in the future.

Neutral Diboron Analogues of Archetypal Aromatic Species by Spontaneous Cycloaddition.

Among the numerous routes organic chemists have developed to synthesize benzene derivatives and heteroaromatic compounds, transition-metal-catalyzed cycloaddition reactions are the most elegant. In contrast, cycloaddition reactions of heavier alkene and alkyne analogues, though limited in scope, proceed uncatalyzed. In this work we present the first spontaneous cycloaddition reactions of lighter alkene and alkyne analogues. Selective addition of unactivated alkynes to boron-boron multiple bonds under ambient conditions yielded diborocarbon equivalents of simple aromatic hydrocarbons, including the first neutral 6 π-aromatic diborabenzene compound, a 2 π-aromatic triplet biradical 1,3-diborete, and a phosphine-stabilized 2 π-homoaromatic 1,3-dihydro-1,3-diborete. DFT calculations suggest that all three compounds are aromatic and show frontier molecular orbitals matching those of the related aromatic hydrocarbons, C6 H6 and C4 H4 (2+) , and homoaromatic C4 H5 (+) .

Synthesis of cyclic diborenes with unprecedented cis-configuration.

The first examples of cis-configured diborenes - and the first cyclic diborenes - are isolated by taking advantage of stabilisation by chelating diphosphine ligands. The diborenes are prepared by a convenient one-pot reductive procedure that circumvents the need for a pre-formed base-adduct of the boron-containing precursor.

A facile and selective route to remarkably inert monocyclic NHC-stabilized boriranes.

Herein we report a facile and selective synthetic route to monocyclic NHC-stabilized boriranes. We have succeeded in obtaining two highly stable new boriranes through salt elimination of NHC-stabilized dichloroboranes with the dianion of trans-stilbene, Na2[C14H12]. One borirane was observed to undergo reaction with [Pt(PEt3)3], in which the Pt(0) center oxidatively adds a backbone C-H bond of the NHC, leading to the isolation of the Pt(II) complex trans-[(Et3P)2PtH{C=CH(NMe)2C·BPh(C14H12)}]. The remarkable inertness of the NHC-boriranes suggests a strong stabilising effect of quaternization of the boron atom.