Synthesis and Characterisation of Novel Main Group Element Clusters with Tin‐Phosphorus, Tin‐Arsenic, and Germanium‐Phosphorus Skeletons

Abstract

The reaction of iPr3SiPLi2 with SnCl2 in the mol ratio 1:1 leads to the formation of [Sn7(PSiiPr3)7] (1). The cluster [Sn8(PSiiPr3)6Cl2] (3) is obtained, if the same reaction is carried out with a slight excess of the metal salt. Similar lithium chloride elimination reactions between SnCl2 and iPr3SiAsLi2 in the mol ratio 1:1 and 2:3, however, yield [Sn7(AsSiiPr3)7] (2) and [Sn4(AsSiiPr3)6Li4(Et2O)2] (4), respectively. The metal salt GeCl2(diox)2 (diox = 1,4‐dioxane) reacts with iPr3SiPLi2 to give [Ge6(PSiiPr3)6] (5). Compounds 1−5 were characterised by NMR and IR spectroscopic techniques as well as elemental analysis. The crystal structures were identified by X‐ray diffraction analysis, which confirmed that the heptameric skeletons of 1 and 2 are structurally analogous. The Sn/P cluster 3 contains subvalent tin atoms, while 4 forms a Sn4As6Li4 rhombododecahedron and 5 a slightly distorted hexagonal prism. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

Würfelspiele im Bereich der Heterokubane: Synthese und Charakterisierung von Molekülverbindungen der Systeme Sn/E und Pb/E (E = P/As)

“…Gruppe untersucht. Während in den Systemen Sn/E (E = P, As) einige Vertreter bekannt sind, [4][5][6][7][8][9][10][11][12] sind Molekülverbindungen des Systems Pb/E sehr selten. [13][14][15][16][17][18] In Abhängigkeit von der Synthesemethode und der Wahl des sterischen Anspruchs der verwendeten Substituenten bilden sich unterschiedliche polyedrische Molekülverbindungen.…”

Phosphines and Related Tervalent Phosphorus Systems

“…A kinetic study has compared the effectiveness of tertiary phosphines and phosphite esters in the catalysis of the cleavage of the silicon-silicon bond of methylchlorodisilanes, providing evidence for the involvement of a stabilised silylene intermediate. 585 The anion of the g-phosphino-b-diketimine (197) has been shown to react with arsenic trichloride to give the phosphinoarsino-b-diketimine (198) 587 a discussion as to whether allylphosphine is a carbon or a phosphorus base in the gas phase, 588 the relative merits of QSAR and QALE correlations in assessing donor properties of tervalent P systems 589 and a new assessment of the stereoelectronic profile of phosphine and phosphite ligands. 590 Trimethylphosphine has been used to probe the acid sites in a dealuminated nanosized zeolite using 31 P CP/MAS NMR and other NMR techniques.…”

“…196 New main group element organophosphide cluster species involving tin and germanium have also been prepared and structurally characterised. 197,198 A range of cyclic, oligomeric gold organophosphides has been prepared by treatment of gold(I) complexes of secondary phosphines with aqueous ammonia. 199,200 The previously established alkali metal cleavage of the P-P bond of tetraphenyl-1,2-dihydrodiphosphetenes to give the diphosphide anion (90) has been used to prepare anionic cyclic organophosphidoplatinum complexes.…”

Germanium/phosphorus cage compounds with germanium in three different oxidation states

“…9 Herein we report the synthesis and characterization of novel 14/15 cage compounds with new structural motifs and with germanium atoms in three different formal oxidation states. In contrast to published synthetic procedures involving reactions between RPH 2 or LiHPR with, for example, Sn(NMe 2 ) 2 , 10 or LiCl elimination reactions using the doubly lithiated species RPLi 2 and dihalides of group 14 elements, 7 we focused on the monolithiated species LitBuPH in reactions with GeCl 2 , which seem to be the key to obtain unprecedented mixed-valence cage compounds.…”

“…7 The only two Ge/P systems known in the literature are the cage compound [(R 2 Ge) 6 P 4 ] (R = CH 3 , C 2 H 5 ), which was synthesized by thermal condensation of R 2 Ge(PH 2 ) 2 , 8 and the hexagonal prismatic [Ge 6 (PSiiPr 3 ) 6 ] obtained from the reaction of GeCl 2 (diox) 2 with Li 2 PSiiPr 3 . 7 To the best of our knowledge, there is no Ge/P cage compound with the germanium atom in different oxidation states. The polymeric 14/16 compound {[Ge 5 Te 10 ] 4À } n is the only example with three different oxidation states of germanium being observed in a single compound.…”