Frustrated Lewis pair-ligated tetrelenes.

The reactivity of [PB{SiX}] (X = Cl, Br; PB = 1,2-Pr(CH)BCy; E = Si, Ge) adducts is described, with an initial focus on reduction attempts to access [PB{E}] species; however, in all cases only free PB ligand was formed as the soluble product. Moreover, computations were performed to evaluate the energy penalty associated with EX dissociation from the PB chelates. Moving up the periodic table, the formal methylene adduct [PB{CH}] was isolated and its reactivity was compared with its heavier element congeners of [PB{EH}].

A Stable Homoleptic Divinyl Tetrelene Series.

The synthesis of the new bulky vinyllithium reagent ( IPr=CH)Li, ( IPr=[(MeCNDipp) C]; Dipp=2,6-iPr C H ) is reported. This vinyllithium precursor was found to act as a general source of the anionic 2σ, 2π-electron donor ligand [ IPr=CH] . Furthermore, a high-yielding route to the degradation-resistant Si precursor IPr⋅SiBr is presented.

Current advances in tin cluster chemistry.

This perspective summarizes highlights and most recent advances in tin cluster chemistry, thereby addressing the whole diversity of (mostly) discrete units containing tin atoms. Although being a (semi-)metallic element, tin is in the position to occur both in formally positive or negative oxidation states in these molecules, which causes a broad range of fundamentally different properties of the corresponding compounds. Tin(iv) compounds are not as oxophilic and not as prone to hydrolysis as related Si or Ge compounds, hence allowing for easier handling and potential application.

[{(PhSn)SnS}{(MCp)S}] (M = W, Mo): Minimal Molecular Models of the Covalent Attachment of Metal Chalcogenide Clusters on Doped Transition Metal Dichalcogenide Layers.

With the aim to mimic the yet unknown covalent deposition of metal chalcogenide clusters on transition metal dichalcogenide (TMDC) MoS or WS layers, and thereby explore the interaction between the two systems and potential consequences on physical properties of the TMDC material, we synthesized heterobimetallic model systems. The heterocubane-type cluster [(SnCl)(WCp)S] (), the organotin-sulfidomolybdate cluster [{(PhSn)SnS}{(MoCp)S}] (), and the corresponding tungstate [(PhSn)SnS{(WCp)S}] () were obtained in ligand exchange reactions from [(PhSn)S] and [M(CO)CpCl]. Indeed, the {MS} cages in - resemble a section of the respective TMDC monolayers, altogether representing minimal molecular model systems for the adsorption of organotin sulfide clusters on MoS or WS.

Controlling the White-Light Generation of [(RSn) E ]: Effects of Substituent and Chalcogenide Variation.

Adamantane-type organotin chalcogenide clusters of the general composition [(RT) S ] (R=aromatic substituent, T=Si, Ge, Sn) have extreme non-linear optical properties that lead to highly directional white-light generation (WLG) upon irradiation with an IR laser diode. However, the mechanism is not yet understood. Now, a series of compounds [(RSn) E ] (R=phenyl, cyclopentadienyl, cyclohexyl, benzyl, CH CH (C H )CO Et; E=S, Se), were prepared, characterized, and investigated for their nonlinear optical properties.

Dinuclear organogermanium chalcogenide complexes as intermediates towards functionalized clusters.

Reactions of R1GeCl3 (R1 = CMe2CH2COMe) with (Me3Si)2E (E = S, Se, Te) yield three new organogermanium chalcogenide complexes [(R1GeCl)2S2] (1), [(R1GeCl)2Se2] (2), and [(R1GeCl)2Te2] (3) with functionalized ligands R1 = CMe2CH2COMe. NMR titration experiments clearly demonstrate that these dimeric complexes are intermediates in the formation of the well-known sesquichalcogenide clusters [(R1Ge)4E6]. In striking contrast to related tin compounds that were recently reported, the mono-bridged complexes of the type "[(R1GeCl2)2E]" and defect-heterocubane-type clusters "[(R1Ge)3E4Cl]" do not form on the NMR time scale for E = S or Te, and only in traces for E = Se.

Transition-Metal-Induced Rearrangement of [(PhSn) S ] Towards Ternary Cu /Sn/S or Cu /Sn/S Clusters.

Direct access of ternary copper-tin sulfide clusters by reactions of a binary organotin sulfide cluster, [(PhSn) S ] (A), with transition metal complexes was achieved for the first time without extra addition of further chalcogenide sources. This indicates that an in situ rearrangement of the inorganic core takes place even without initial formation of anionic fragments. The use of [Cu(PPh ) Cl] or [Cu(PPh ) Cl ] as reactants yielded the ternary clusters [(CuPPh ) (PhSn) Cu S Cl ] (1) and [{Cu(PPh ) } (PhSn) (SnCl)S ] (2), respectively.

Syntheses and Properties of Gold-Organotin Sulfide Clusters.

We report that reactions of the binary organotin sulfide cluster [(RSn)S]Cl [A; R = CMeCHC(O)Me] with gold(I) phosphane complexes yield discrete ternary complexes [(RSn)(AuPMe)S] (1) and [(RSn)(AuPMe)S] [2; R = CMeCHC(NNH)Me], which are related to recently published complexes [(RSn)(AuPPh)S] (B and C). Further, we present a binary tin sulfide cluster that cocrystallizes with a structure-directing salt of a gold phosphane complex in [Au(dppe)][(RSn)SCl] [3; R = CMeCHC(NNHPh)Me]. The nature of the product depends on the choice of the phosphane ligand as well as the addition of hydrazine hydrate or phenylhydrazine.

Organotetrel Chalcogenide Clusters: Between Strong Second-Harmonic and White-Light Continuum Generation.

Highly directional white-light generation was recently reported for the organotin sulfide cluster [(StySn)S] (Sty = p-styryl). This effect was tentatively attributed to the amorphous nature of the material in combination with the specific combination of an inversion-symmetry-free T/E cluster core (T = tetrel, E = chalcogen) with the attachment of ligands that allow π delocalization of the electron density. Systematic variation of T and the organic ligand (R) that runs from T = Si through Ge to Sn and from R = methyl through phenyl and p-styryl to 1-naphthyl provides a more comprehensive view.