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Synthesis of 2,2′,5,5′‐Tetraphenyl‐1,1′‐diarsacalcocene and ‐strontocene
Author(s) -
Westerhausen Matthias,
Birg Christin,
Piotrowski Holger
Publication year - 2000
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 - 10.1002/1099-0682(200010)2000:10<2173::aid-ejic2173>3.0.co;2-y
Subject(s) - chemistry , tetrahydrofuran , strontium , metalation , toluene , solvent , medicinal chemistry , trimethylsilyl , polymer chemistry , inorganic chemistry , organic chemistry
The metalation of H 2 As−Si i Pr 3 with bis(tetrahydrofuran‐ O )calcium‐ and ‐strontium bis[bis(trimethylsilyl)amide] yields tetrakis(tetrahydrofuran‐ O )calcium‐ ( 1a ) and ‐strontium bis(triisopropylsilylarsanide) ( 2a ). These compounds are in equilibrium with their dimers 1b (Ca) and 2b (Sr) by elimination of THF. The addition of diphenylbutadiyne to a THF/toluene solution of 1 and 2 gives bis(tetrahydrofuran‐ O )calcium‐ ( 3 ) and ‐strontium bis(2,5‐diphenylarsolide) ( 4 ). The proposed reaction mechanism explains the formation of the ( i Pr 3 Si) 2 As − and 2,5‐diphenyl‐3,4‐bis(phenylethynyl)arsolide anions based on an intermolecular H/Si i Pr 3 exchange reaction. The latter anion was characterized by X‐ray crystallography with the binuclear cation [(THF) 3 Ca{µ‐As(H)Si i Pr 3 } 3 Ca(THF) 3 ] + ( 5 ). The arsolide ligands of 3 and 4 are η 5 ‐bonded to the metal centers, whereas 5 crystallizes as a solvent‐separated ion pair.