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.
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...
A general route for the selective preparation of diaryltin dichlorides, dibromides, and diiodides from readily accessible but sterically demanding, 2,6-disubstituted or 2,4,6-trisubstituted aryl Grignard reagents ArylMgBr and tin tetrachloride was developed. During work-up, the initially obtained [a] MSc, 2591 Scheme 1. Selection of commonly employed synthetic methods for the preparation of diaryltin dihalides Aryl 2 SnX 2 . (X = Cl, Br, I).
Palladium and platinum boratrane complexes of the type [M{B(Pn)}(PPh)] (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 KTn 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(Pn)}(PPh)H]Cl (2a), which after reaction with a base gave 2b. Subsequent oxidation with Br and I, respectively, led to the dihalide compounds of the molecular formula [M{B(Pn)}X] (3a,b-4a,b). Halide abstraction with Ag(SbF) further gave interesting cationic compounds of either dimeric [Pd{B(Pn)}X](SbF) (5a,b) or monomeric [Pd{B(Pn)}(NCMe)](SbF) (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.
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