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Dichlorogermylene‐Alkyldichlorophosphane Reactions Revisited: Characterisation of Bis(trichlorogermyl)phosphanes, Trichlorogermyldiphosphanes, and Ge‐P Heterocycles
Author(s) -
Karnop Michael,
Mont WolfWalther Du,
Jones Peter G.,
Jeske Jörg
Publication year - 1997
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19971301109
Subject(s) - chemistry , germanium , ionic bonding , reaction conditions , medicinal chemistry , isopropyl , stereochemistry , organic chemistry , catalysis , ion , silicon
The reactions of alkyldichlorophosphanes 1 (RPCl 2 ; R = tert ‐butyl: 1a , R = isopropyl; 1b , R = 1‐adamantyl: 1c ) with the germanium dichloride dioxane complex were followed by 31 P NMR. Depending on the organic substituents and the reaction conditions, mixtures of trichlorogermylphosphanes RP(GeCl 3 ) 2 4a‐c , RPHGeCl 3 5a‐c , diphosphanes R(H)PP(H)GeCl 3 6a‐c , R(Cl)PP(H)GeCl 3 7a, b cyclophosphanes, and Ge‐P heterocycles such as triphosphadigermolanes (RP) 3 (GeCl 2 ) 2 8a, b and tetraphosphagermolane (RP) 4 )GeCl 2 10b are formed. As a further unexpected byproduct of the reaction of 1a with GeCl 2 –dioxane, a small amount of tri‐ tert ‐butyl(trichlorogermyl)cyclotetraphosphane 9a was isolated. From the reaction of 1c with two equivalents of GeCl 2 –dioxane, separation from byproducts 5c and 6c by crystallisation furnished colourless crystals of 4c (R = 1‐adamantyl) as the first pure organylbis(trichlorogermyl)phosphane. Surprisingly, the reaction of isoprophyl phosphane with germanium tetrachloride, intended to prepare 5a , led to crystalline isopropylphosphonium trichlorogermanate(II) 11 . The structures of molecular 4c and 9a and ionic 11 were determined by X‐ray crystallography.