Strong Closed-Shell Interactions in Inorganic Chemistry.

Small inorganic rings in the 21st century: from fleeting intermediates to novel isolable entities.

http://users.auth.gr/akrivos/Metaptyxiaka/Proxorimeni%20Anorgani/Coord_Chem_Rev_236_2003_35.pdf

Chemistry of arsenic, antimony and bismuth compounds derived from xanthate, dithiocarbamate and phosphorus based ligands

There has been much interest in the synthesis and properties of doubly bonded systems between heavier Group 15 elements, i. e. heavier analogues of azo-compounds (dipnictenes), from the viewpoints of fundamental and material chemistry. Although such double-bond compounds between heavier main group elements are known to be highly reactive, too much so to be isolated as stable compounds, a number of reports on the synthesis of kinetically stabilized diphosphenes (RPPR), diarsenes (RAsAsR), and phosphaarsenes (RPAsR) bearing bulky substituent have been published since 1980. We have also succeeded in the synthesis of the first stable distibene (RSbSbR) and dibismuthene (RBiBiR) by taking advantage of efficient steric protection groups, 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl (Tbt) and 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl (Bbt), and revealed their structures and properties systematically. Thus, the doubly bonded compounds between heavier Group 15 elements are no longer imaginary species but are those with real existence which are stable, even in the case of the heaviest non-radioactive element bismuth, when they are appropriately protected by bulky substituents. This Perspective describes our research on the chemistry of kinetically stabilized double-bond compounds between heavier Group 15 elements.

Doubly bonded systems between heavier Group 15 elements.

Stable compounds containing heavier group 15 elements in the +1 oxidation state

Syntheses and structures of isopropyl- and [bis(trimethylsilyl)methyl]antimony rings and catena-tri- and catena-tetrastibines by reaction of organoantimony rings with distibines

Synthesis, spectroscopic characterization and molecular structure of dimeric (diethyldithiophosphinatod)DI(para-tolyl) antimonyl(III), [(p-CH3C6H4)2SbS2P(C2H5)2]2, containing a novel monocyclic P2S4Sb2 inorganic ring system, formed through Sb…S semibonding interactions

Synthesis of (Me3SiCH2Sb)n and reactions with ditellurides: crystal structure of [Cp2Co][Me3SiCH2SbCl3]

Reactions of (MesSb)4 or (EtSb)x with (MeSe)2, (PhSe)2, (MeTe)2, (PhTe)2 or (p-TolTe)2 were studied in C6D6 in sealed NMR tubes. Products of the type Mes2 SbER (E = Se, Te; R = Me, Ph, p-Tol) and (p-TolTe)2 SbMes or Et (SbER)2 (E = Se, Te; R = Me, Ph, p-Tol) were obtained. EtSb(TePh)2 was synthesized as red crystals. The telluro stibanes Me2 SbTePh and Et2 SbTePh were prepared from Me4 Sb2 or Et4 Sb2 and (PhTe)2.

Reactions of Cyclostibanes or Distibanes with Diselenides or Ditellurides

Elimination of Me3SiCH2Br from (Me3SiCH2)3SbBr2 leads to (Me3SiCH2)2SbBr ( 1 ). Reaction of 1 with Mg in tetrahydrofuran gives [(Me3SiCH2)2Sb]2 ( 2 ). Complete exchange reactions of 2 with RTeTeR afford (Me3SiCH2)2 SbTeR ( 3 : R = Ph, 4 : R = p-Tol). [(Me3SiCH2)2Sb]2Te ( 5 ) is formed by insertion of Te into 2 or better by the reaction of 1 with Na2Te. Die Eliminierung von Me3SiCH2Br aus (Me3SiCH2)3SbBr2 fuhrt zu (Me3SiCH2)2SbBr ( 1 ). Die Reaktion von 1 mit Mg in Tetrahydrofuran ergibt [(Me3SiCH2)2Sb]2 ( 2 ). Durch vollstandige Austauschreaktionen von 2 mit RTeTeR wird (Me3SiCH2)2SbTeR ( 3 : R = Ph, 4 : R = p-Tol) synthetisiert. [(Me3SiCH2)2Sb]2Te ( 5 ) wird durch Insertion von Te in 2 oder besser durch Umsetzung von 1 mit Na2Te gebildet.

R. Kaller

Papers

Syntheses and structures of isopropyl- and [bis(trimethylsilyl)methyl]antimony rings and catena-tri- and catena-tetrastibines by reaction of organoantimony rings with distibines

Synthesis, spectroscopic characterization and molecular structure of dimeric (diethyldithiophosphinatod)DI(para-tolyl) antimonyl(III), [(p-CH3C6H4)2SbS2P(C2H5)2]2, containing a novel monocyclic P2S4Sb2 inorganic ring system, formed through Sb…S semibonding interactions

Synthesis of (Me3SiCH2Sb)n and reactions with ditellurides: crystal structure of [Cp2Co][Me3SiCH2SbCl3]

Reactions of Cyclostibanes or Distibanes with Diselenides or Ditellurides

Synthese von tetrakis-(trimethylsilylmethyl)distiban und reaktionen mit ditelluriden oder tellur