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Synthesis and Homomolecular Metalation of Trialkylsilylphosphanides of Calcium and Barium
Author(s) -
Westerhausen Matthias,
H. Digeser Matthias,
Krofta Mathias,
Wiberg Nils,
Nöth Heinrich,
Knizek Jörg,
Ponikwar Werner,
Seifert Thomas
Publication year - 1999
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199905)1999:5<743::aid-ejic743>3.0.co;2-1
Subject(s) - tetrahydrofuran , chemistry , metalation , homoleptic , tetrahydropyran , trimethylsilyl , medicinal chemistry , trigonal bipyramidal molecular geometry , amide , barium , alkoxide , toluene , tetramer , stereochemistry , molecule , inorganic chemistry , metal , organic chemistry , solvent , catalysis , ring (chemistry) , enzyme
Metalation of triisopropylsilylphosphane with bis(tetrahydrofuran‐ O )calcium bis[bis(trimethylsilyl)amide] in tetrahydropyran (thp) in a molar ratio of 3:2 yields (Me 3 Si) 2 NCa[μ‐P(H)Si i Pr 3 ] 3 Ca(thp) 3 ( 1 ) containing a trigonal‐bipyramidal Ca 2 P 3 core, the metal atoms occupying apical positions. Reaction of two equivalents of triisopropylsilylphosphane or ‐arsane with bis(tetrahydrofuran‐ O )barium bis[bis(trimethylsilyl)amide] in tetrahydrofuran gives the corresponding bis(phosphanide) 2 and bis(arsanide) 3 , compounds of the type (thf) 3 Ba[μ‐E(H)Si i Pr 3 ]Ba(thf) 2 E(H)Si i Pr 3 with E = P, As. The equimolar reaction of (tri‐ tert ‐butylsilyl)phosphane with (thf) 2 Ba[N(SiMe 3 ) 2 ] 2 in toluene yields heteroleptic dimeric (thf) 2 Ba[N(SiMe 3 ) 2 ][P(H)Si t Bu 3 ] ( 4 ). Addition of a further equivalent of H 2 PSi t Bu 3 leads to the formation of homoleptic (thf) n Ba[P(H)Si t Bu 3 ] 2 ( 5 ). Dissolution of the latter in aromatic hydrocarbons leads to the elimination of H 2 PSi t Bu 3 , yielding dimeric (thf)Ba 3 (PSi t Bu 3 ) 2 [P(H)Si t Bu 3 ] 2 ( 6 ). The inner core of 6 consists of the tetramer (BaPSi t Bu 3 ) 4 based on a Ba 4 P 4 heterocubane unit, two opposite faces being capped with (thf)Ba[P(H)Si t Bu 3 ] 2 molecules.