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Oligomeric Solvent‐Free Magnesium Bis(phosphanides) − Molecular Structure of Trimeric Magnesium Bis[bis(trimethylsilyl)phosphanide]
Author(s) -
Westerhausen Matthias,
Digeser Matthias H.,
Wieneke Birgit,
Nöth Heinrich,
Knizek Jörg
Publication year - 1998
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(199804)1998:4<517::aid-ejic517>3.0.co;2-d
Subject(s) - chemistry , trimer , dimer , magnesium , toluene , trimethylsilyl , metathesis , monomer , molecule , solvent , benzene , crystallography , inorganic chemistry , polymer chemistry , medicinal chemistry , organic chemistry , polymerization , polymer
The metathesis reaction of (dme)LiPH 2 and chlorodiisopropylsilane yields HP(SiH i Pr 2 ) 2 ( 1 ) and P(SiH i Pr 2 ) 3 ( 2 ). The metalation of 1 by n/sec ‐dibutylmagnesium in heptane leads to the formation of dimeric magnesium bis[bis(diisopropylsilyl)phosphanide] [( 3 ) 2 ]. A toluene solution of magnesium bis[bis(trimethylsilyl)phosphanide] ( 4 ) shows a dimer‐trimer equilibrium in the 31 P{ 1 H}‐NMR spectrum at −40°C with an increasing amount of the dimer with increasing temperature. A molecular mass determination by freezing‐point depression in benzene yields a value of 516 g·mol −1 , which lies between a monomeric and a dimeric molecule. Cooling of the toluene solution to −30°C leads to the precipitation of single crystals of monoclinic {(Me 3 Si) 2 P−Mg[μ‐P(SiMe 3 ) 2 ] 2 } 2 Mg [( 4 ) 3 ].