Intramolecularly O,N,O-Coordinated Tin(II) Salts: Syntheses, Structures, Cyclization, and Transition Metal Complexation.

We report the syntheses of tin(II) salts of the types [L1SnX]SnX3 [L1=2,6-{(i-PrO)2(O)P}2C5H3N: 1, X=Cl; 2, X=Br], [L2SnCl]SnCl3 [L2=2-{(i-PrO)Ph(O)P}-6-{(i-PrO)2(O)P}C5H3N: 3], [L3SnX]SnX3 [L3=2,6-{MeO(O)C}2C5H3N: 4, X=Cl; 5, X=Br], [L4SnX]SnX3 [L4=2,6-{Et2N(O)C}2C5H3N: 6, X=Cl; 7, X=Br]. These compounds were obtained by addition of SnX2 to the corresponding ligand inducing autoionization of the respective tin(II) halide. The thermal stability of 1, 3, and 4 was elucidated, giving, under ester cleavage and cyclisation, the tin(II) derivatives 8-12. The reaction of [L1SnCl]SnCl3 (1) with W(CO)4(thf)2 afforded the tungsten tetracarbonyl complex [{L1SnCl}{SnCl3}W(CO)4] (13), representing the first example in which a tin(II) stannate anion and a tin(II) stannylium cation simultaneously coordinate to a transition metal centre. The compounds were characterized by single crystal X-ray diffraction analyses and in part by elemental analyses, IR and NMR spectroscopy, electrospray ionization mass spectrometry. DFT calculations accompany the experimental work.

Synthesis, Structure and Application of Intramolecularly-Coordinated Gallium Chalcogenides: Suitable Single-Source precursors for Gax Sey Materials.

Studies have been focused on the synthesis of N→Ga-coordinated organogallium selenides and tellurides [L1 Ga(µ-Se)]2 (1), [L2 Ga(µ-Se)]2 (2) and [L1 Ga(µ-Te)]2 (3), respectively, containing either N,C,N- or C,N-chelating ligands L1, 2 (L1 is {2,6-(Me2 NCH2 )2 C6 H3 }- and L2 is {2-(Et2 NCH2 )-4,6-tBu2 -C6 H2 }- ) having Ga/E (E=Se or Te) atoms in 1/1 ratio. To change the Ga/E ratio, an unusual N→Ga-coordinated organogallium tetraselenide L1 Ga(κ2 -Se4 ) (4) was prepared. An unprecedented complex (L1 Ga)2 (µ-Te2 )(µ-Te) (5), as the result of the non-stability of 3, was also isolated. Compound 2 is a suitable single-source precursor for the preparation of amorphous GaSe thin films by the spin coating. Moreover, simple heating of an octadecylamine solution of 2 provided, after work up, monoclinic Ga2 Se3 crystals with different crystallinity according to conditions used. Therefore, compound 2 may be also used as a source of Ga2 Se3 in the low-temperature doping process of Bi2 Se3 .

Intramolecularly Coordinated Gallium Sulfides: Suitable Single Source Precursors for GaS Thin Films.

Our studies have been focused on the synthesis of N→Ga coordinated organogallium sulfides [L1 Ga(µ-S)]3 (1) and [L2 Ga(µ-S)]2 (2) containing either N,C,N- or C,N-chelating ligands L1 or L2 (L1 is {2,6-(Me2 NCH2 )2 C6 H3 }- and L2 is {2-(Et2 NCH2 )-4,6-tBu2 -C6 H2 }- ). As the result of the different ligands, compounds 1 and 2 differ mutually in their structure. To change the Ga/S ratio, unusually N→Ga coordinated organogallium tetrasulfide L1 Ga(κ2 -S4 ) (3) was prepared and the unprecedented complex [{2-[CH{(CH2 )3 CH3 }(µ-OH)]-6-CH2 NMe2 }C6 H3 ]GaS (4) was also isolated as the minor by-product of the reaction. Compounds 1-3 were further studied as potential single-source precursors for amorphous GaS thin film deposition by spin-coating.

Synthesis and Application of Monomeric Chalcogenolates of 13†Group Elements.

Utilization of the N,C,N-chelating ligand L (L={2,6-(Me2 NCH2 )2 C6 H3 }- ) in the chemistry of 13 group elements provided either N→In coordinated monomeric chalcogenides LIn(µ-E4 ) (E=S, Se) with unprecedented InE4 inorganic ring or monomeric chalcogenolates LM(EPh)2 (M=Ga, In). Complex LGa(SePh)2 was selected as the most suitable single source precursor (SSP) for the deposition of amorphous semiconducting GaSe thin films using spin coating method.