A Sterically Accessible Monomeric Stibine Oxide Activates Organotetrel(IV) Halides, Including C-F and Si-F Bonds.

Phosphine oxides and arsine oxides are common laboratory reagents with diverse applications that stem from the chemistry exhibited by these monomeric species. Stibine oxides are, in contrast, generally dimeric or oligomeric species because of the reactivity-quenching self-association of the highly polarized stiboryl (Sb=O/Sb+-O-) group. We recently isolated Dipp3SbO (Dipp = 2,6-diisopropylphenyl), the first example of a kinetically stabilized monomeric stibine oxide, which exists as a bench-stable solid and bears an unperturbed stiboryl group. Herein, we report the isolation of Mes3SbO (Mes = mesityl), in which the less bulky substituents maintain the monomeric nature of the compound but unlock access to a wider range of reactivity at the unperturbed stiboryl group relative to Dipp3SbO. Mes3SbO was found to be a potent Lewis base in the formation of adducts with the main-group Lewis acids PbMe3Cl and SnMe3Cl. The accessible Lewis acidity at the Sb atom results in a change in the reactivity with GeMe3Cl, SiMe3Cl, and CPh3Cl. With these species, Mes3SbO formally adds the E-Cl (E = Ge, Si, C) bond across the unsaturated stiboryl group to form a 5-coordinate stiborane. The biphilicity of Mes3SbO is sufficiently potent to activate even the C-F and Si-F bonds of C(p-MeOPh)3F and SiEt3F, respectively. These results mark a significant contribution to an increasingly rich literature on the reactivity of polar, unsaturated main-group motifs. Furthermore, these results highlight the utility of a kinetic stabilization approach to access unusual bonding motifs with unquenched reactivity that can be leveraged for small-molecule activation.

Recent advances in the stabilization of monomeric stibinidene chalcogenides and stibine chalcogenides.

The elucidation of novel bonding situations at heavy p-block elements has greatly advanced recent efforts to access useful reactivity at earth-abundant main-group elements. Molecules with unsaturated bonds between heavier, electropositive elements and lighter, electronegative elements are often highly polarized and competent in small-molecule activations, but the reactivity of these molecules may be quenched by self-association of monomers to form oligomeric species where the polar, unsaturated groups are assembled in a head-to-tail fashion. In this Frontier, we discuss the synthetic strategies employed to isolate monomeric σ2,λ3-stibinidene chalcogenides (RSbCh) and monomeric σ4,λ5-stibine chalcogenides (R3SbCh). These classes of molecules each feature polarized antimony-chalcogenide bonds (Sb = Ch/Sb+-Ch-). We highlight how the synthesis and isolation of these molecules has led to the discovery of novel reactivity and has shed light on fundamental aspects of inorganic structure and bonding. Despite these advances, there are critical aspects of this chemistry that remain underdeveloped and we provide our perspective on yet-unrealized synthetic targets that may be achieved with the continued development of the strategies described herein.

Silver 2,4'-Bipyridine Coordination Polymer for the High-Capacity Trapping of Perrhenate, A Pertechnetate Surrogate.

Pertechnetate, the most stable form of the radionuclide 99Tc in aerobic aqueous systems, is a hazardous anion present in nuclear waste. Its high mobility in water makes the remediation of the anion challenging. In the past decade, significant effort has been placed into finding materials capable of adsorbing this species. Here, we present the synthesis and high-resolution crystal structure of the coordination polymer [Ag(2,4'-bipyridine)]NO3, which is capable of sequestering perrhenate─a pertechnetate surrogate─through anion exchange to form another new coordination polymer, [Ag(2,4'-bipyridine)]ReO4. Both the beginning and end structures were solved by single-crystal X-ray diffraction and the adsorption reaction was monitored through inductively coupled plasma-optical emission spectroscopy and UV-vis spectroscopy. The exchange reaction follows a pseudo-second-order mechanism and the maximum adsorption capacity is 764 mg ReO4/g [Ag(2,4'-bipyridine)]NO3, one of the highest recorded for a coordination polymer or metal-organic framework. A solvent-mediated recrystallization mechanism was determined by monitoring the ion-exchange reaction by scanning electron microscopy-energy-dispersive spectroscopy and powder X-ray diffraction.

Variation in pnictogen-oxygen bonding unlocks greatly enhanced Brønsted basicity for the monomeric stibine oxide.

Phosphine oxides and arsine oxides feature highly polarized pnictoryl groups (Pn+-O-/Pn = O; Pn = P, As) and react as Brønsted bases through O-centered lone pairs. We recently reported the first example of a monomeric stibine oxide, Dipp3SbO (Dipp = diisopropylphenyl), allowing periodic trends in pnictoryl bonding to be extended to antimony for the first time. Computational studies suggest that, as the pnictogen atom becomes heavier, delocalization of electron density from the O-centered lone pairs to the Pn-C σ* orbitals is attenuated, destabilizing the lone pairs and increasing the donor capacity of the pnictine oxide. Herein, we assess the Brønsted basicity of a series of monomeric pnictine oxides (Dipp3PnO; Pn = P, As, and Sb). Stoichiometric reactivity between Dipp3PnO and a series of acids demonstrates the greatly enhanced ability of Dipp3SbO to accept protons relative to the lighter congeners, consistent with theoretical isodesmic reaction enthalpies and proton affinities. 1H NMR spectrometric titrations allow for the pKaH,MeCN determination of Dipp3AsO and Dipp3SbO, revealing a 106-fold increase in Brønsted basicity from Dipp3AsO to Dipp3SbO. The increased basicity can be exploited in catalysis; Dipp3SbO exhibits dramatically increased catalytic efficiency in the Brønsted base-catalyzed transesterification between p-nitrophenyl acetate and 2,2,2-trifluoroethanol. Our results unambiguously confirm the drastic increase in Brønsted basicity from Dipp3PO < Dipp3AsO < Dipp3SbO, a direct consequence of the variation in the electronic structure of the pnictoryl bond as the pnictogen atom increases in atomic number.

Isolation, bonding and reactivity of a monomeric stibine oxide.

In contrast to phosphine oxides and arsine oxides, which are common and exist as stable monomeric species featuring the corresponding pnictoryl functional group (Pn=O/Pn+-O-; Pn = P, As), stibine oxides are generally polymeric, and the properties of the unperturbed stiboryl group (Sb=O/Sb+-O-) remain unexplored. We now report the isolation of the monomeric stibine oxide, Dipp3SbO (where Dipp = 2,6-diisopropylphenyl). Spectroscopic, crystallographic and computational studies provide insight into the nature of the Sb=O/Sb+-O- bond. Moreover, isolation of Dipp3SbO allows the chemistry of the stiboryl group to be explored. Here we show that Dipp3SbO can act as a Brønsted base, a hydrogen-bond acceptor and a transition-metal ligand, in addition engaging in 1,2-addition, O-for-F2 exchange and O-atom transfer. In all cases, the reactivity of Dipp3SbO differed from that of the lighter congeners Dipp3AsO and Dipp3PO.

H-Atom Assignment and Sb-O Bonding of [Mes3SbOH][O3SPh] Confirmed by Neutron Diffraction, Multipole Modeling, and Hirshfeld Atom Refinement.

Neutron wavelength-resolved Laue diffraction experiments permit accurate refinement of the H-atom positions and anisotropic displacement parameters of [Mes3SbOH][O3SPh]. A multipole-based charge density refinement and a topological analysis of the refined electron density were also performed. Hirshfeld atom refinement (HAR) recovers the neutron-determined H-atom parameters, and the quantum-mechanical electron density used in HAR recovers the electron density topology from the refined multipole model. These results confirm that [Mes3SbOH][O3SPh] does indeed feature a hydroxystibonium cation with a nominal Sb-O single bond and not a stibine oxide with an Sb=O/Sb+-O- bond.

Unsupported monomeric stibine oxides (R3SbO) remain undiscovered.

Attempts to investigate the properties and reactivity of the stiboryl moiety (R3Sb+-O- or R3Sb[double bond, length as m-dash]O), as in monomeric stibine oxides free of interaction with Lewis acids/bases, led us to conclude that this functional group remains undiscovered. X-ray crystallographic, computational, and spectroscopic data indicate that previously proposed H-bonded stibine oxide adducts Mes3SbOHO3SR are in fact hydroxystibonium salts [Mes3SbOH][RSO3].

Analysis of Oxygen-Pnictogen Bonding with Full Bond Path Topological Analysis of the Electron Density.

A variety of methods are available to investigate the bonding in inorganic compounds. In contrast to wavefunction-based analyses, topological analysis of the electron density affords the advantage of analyzing a physical observable: the electron density. Classical topological analyses of bonding interactions within the atoms in molecules framework typically involve location of a bond path between two atoms and evaluation of a range of real-space functions at the (3, -1) critical point in the electron density that exists on that bond path. We show here that counter-intuitive trends are obtained from the analysis of the electron density (ρ), the Laplacian (∇2ρ), and ellipticity (ε) at the O-E (3, -1) critical points in the coupled-cluster singles doubles electron densities of a series of compounds featuring a range of oxygen-pnictogen bond types: EO+, HEO, H2EOH, H3EOH+, and H3EO (where E = N, P, As, Sb, or Bi). If, instead, these real-space functions are evaluated along the length of the bond path, the discrepancies in the trends are resolved. We show that robust results are also obtained using electron densities from less computationally demanding density functional theory calculations. The increased computational efficiency allowed us to also investigate organic derivatives of these oxygen-pnictogen-bonded compounds and observe that the trends hold in these instances as well. We anticipate that these results will be of use to inorganic chemists engaged in the synthesis and evaluation of novel bonding interactions, particularly those involving heavy main-group elements.