An Air-Stable Storage Compound for White Phosphorus: Reversible Addition to a Stannylene and Chemical Release of P4.

Controlled insertion into a single P-P bond of white phosphorus (P4) was achieved by employing a diaryl stabilized stannylene, Ar*2Sn (Ar*=2,6-bis(benzhydryl)-4-iPr-phenyl). Conversions of the stannylene with P4 gave a non-pyrophoric, air-stable storage compound, which releases P4 quantitively upon irradiation with light (354 or 455 nm). Alternatively, the phosphorus cage is detached by reacting the storage compound with PhChChPh (Ch=Se, Te). Despite the recent advances in the directed conversion of P4 using main group element compounds, Ar*2Sn constitutes only the second structurally characterized example of a stannylene capable of performing controlled, reversible addition and release of white phosphorus.

From organotin hydrides to heteronuclear main group metal compounds: isolation of the first neutral bismuth/tin clusters.

From conversions of Ar2SnH2 (Ar = Tripp, Dipp; Tripp = 2,4,6-Triisopropylphenyl, Dipp = 2,6-Diisopropylphenyl), and a bismuth(III) amide, Bi[N(SiMe3)2]3, we isolated the first representatives of mixed, uncharged Bi/Sn clusters, Bi8Sn3Ar6. Along with unprecedented bicyclo[2.2.0]hexanes, (HAr2Sn)2Sn2Bi4, these have been characterized by single crystal X-Ray diffraction, heteronuclear NMR, vibrational and UV-Vis spectroscopy. Quantum-chemical calculations were carried out in order to understand bonding within the isolated polyhedral compounds.

Diaryltin Dihydrides and Aryltin Trihydrides with Intriguing Stability.

In the last few decades, organotin hydrides have proven their potential as building blocks for a great variety of organometallic compounds. In this context, organotin hydrides with sterically shielding aryl substituents have attracted special interest, as these ligands can kinetically stabilize metastable products. The selective synthesis of aryltin halide compounds Ar*2SnCl2 and Ar*SnI3 featuring the highly sterically encumbered aryl ligand Ar* (iPrAr* = 2,6-(Ph2CH)2-4-iPrC6H2; MeAr* = 2,6-(Ph2CH)2-4-MeC6H2) is presented. These aryltin halides were converted into corresponding aryltin hydrides Ar*2SnH2 and Ar*SnH3, which exhibit a surprisingly high thermal stability and oxygen tolerance.

Reductive dehydrocoupling of diphenyltin dihydride with LiAlH4: selective synthesis and structures of the first bicyclo[2.2.1]heptastannane-1,4-diide and bicyclo[2.2.2]octastannane-1,4-diide.

The reaction of diphenyltin dihydride with LiAlH4 gives access to a set of charged tin cages as their lithium salts. Variation in the ratio of reactants provides a perstannabicyclooctane dianion and a perstannanorbornane as the di- and monoanions. These compounds can be synthesised selectively by careful stoichiometric control and have been characterised by single crystal X-ray diffractometry, NMR and UV-vis spectroscopy. Computational exploration of the electronic structures of these compounds was undertaken and, in agreement with structural and spectroscopic features, indicated significant σ-delocalisation in the tin skeletons.

Thiopyridazine-Based Palladium and Platinum Boratrane Complexes.

Palladium and platinum boratrane complexes of the type [M{B(PnMe, tBu)3}(PPh3)] (M = Pd 1, Pt 2b) have been prepared via the reaction of the soft scorpionate ligand potassium tris(4-methyl-6- tert-butyl-3-thiopyridazinyl)borate KTnMe, tBu with bis(triphenylphosphine)metal(II) dichloride. While reaction with the Pd precursor allowed direct isolation of a symmetric boratrane complex, the Pt analogue led to the hydrido compound [Pt{B(PnMe, tBu)3}(PPh3)H]Cl (2a), which after reaction with a base gave 2b. Subsequent oxidation with Br2 and I2, respectively, led to the dihalide compounds of the molecular formula [M{B(PnMe, tBu)3}X2] (3a,b-4a,b). Halide abstraction with Ag(SbF6) further gave interesting cationic compounds of either dimeric [Pd{B(PnMe, tBu)3}X]2(SbF6)2 (5a,b) or monomeric [Pd{B(PnMe, tBu)3}(NCMe)2](SbF6) (6) nature. All compounds were spectroscopically and X-ray crystallographically characterized revealing strong metal to boron interactions. DFT calculations of 1, 2a, and 2b confirm the strong M-B interaction and a high positive charge on the metal centers.