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Investigations of LiP(SiMe 2 CH 2 SiMe 3 )–P t Bu 2 , the Surprising Byproduct in the Metalation of (Me 3 Si) 2 P–P t Bu 2
Author(s) -
Sattler Ewald,
Szilvási Tibor,
Matern Eberhard,
Bombicz Petra,
Gamer Michael,
Okrut Alexander,
Kovács Ilona
Publication year - 2017
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/ejic.201701077
Subject(s) - chemistry , metalation , substituent , solid state , stereochemistry , crystallography , medicinal chemistry , crystal structure , solvent , yield (engineering) , x ray crystallography , diffraction , organic chemistry , materials science , physics , optics , metallurgy
During the metalation reaction of (Me 3 Si) 2 P–P t Bu 2 with n BuLi, a byproduct with the sum formula Li(thf) n P(SiMe 2 CH 2 SiMe 3 )–P t Bu 2 ( 2 , n = 2.7–1) was detected. The formation of the unexpected substituent SiMe 2 CH 2 SiMe 3 was investigated, a possible reaction mechanism based on DFT calculations established, and the compound synthesized following an independent route. Compound 2 eliminated thf in vacuo to yield the dimeric [Li(thf)P(SiMe 2 CH 2 SiMe 3 )–P t Bu 2 ] 2 ( 2a ). Exchange of thf with tmeda [Me 2 N(CH 2 ) 2 NMe 2 ] in 2 led to the solvent‐separated ion pair [Li(tmeda) 2 ] + [(SiMe 2 CH 2 SiMe 3 )P–P t Bu 2 ] – ( 4 ). The solid‐state structures of 2a , 4 , and the contact ion pair Li(thf)(tmeda)P(SiMe 2 CH 2 SiMe 3 )–P t Bu 2 ( 5 ) were determined by single‐crystal X‐ray diffraction analysis. Extensive variable‐temperature multinuclear NMR studies were carried out to elucidate the structures of these compounds in solution and to compare them with the solid‐state structures.