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Carbynehydrido‐ and Vinylidenehydridoosmium Complexes with Os(PCy 3 ) 2 as a Molecular Unit
Author(s) -
Werner Helmut,
Jung Stefan,
Weberndörfer Birgit,
Wolf Justin
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(199906)1999:6<951::aid-ejic951>3.0.co;2-u
Subject(s) - chemistry , cationic polymerization , yield (engineering) , medicinal chemistry , stereochemistry , crystallography , organic chemistry , metallurgy , materials science
The reaction of OsCl 3 · 2H 2 O with PCy 3 leads under reducing conditions either to [OsH 6 (PCy 3 ) 2 ] ( 1 ) or [OsH 2 Cl 2 (PCy 3 ) 2 ] ( 2 ). Treatment of 2 with terminal alkynes HC≡CR (R = Ph, SiMe 3 ) affords the carbynehydrido complexes [OsHCl 2 (≡CCH 2 R)(PCy 3 ) 2 ] ( 4 , 5 ), of which 5 (R = SiMe 3 ) is easily converted with traces of water into [OsHCl 2 (≡CCH 3 )(PCy 3 ) 2 ] ( 6 ). Compound 4 (R = Ph) reacts with NaOMe to yield the vinylidenehydridoosmium(II) complex [OsHCl(=C=CHPh)(PCy 3 ) 2 ] ( 7 ) which upon treatment with HBF 4 /OEt 2 gives the five‐coordinate cationic species [OsHCl(≡CCH 2 Ph)(PCy 3 ) 2 ]‐BF 4 ( 8 ). The reaction of [OsH 3 Cl(PCy 3 ) 2 ] ( 9 ) with HC≡CC(CH 3 ) 2 Cl affords a mixture of [OsHCl 2 (≡CCH=CMe 2 )(PCy 3 ) 2 ] ( 10 ) and [OsCl 2 (H 2 )(=CHCH=CMe 2 )(PCy 3 ) 2 ] ( 11 ). Compound 11 is quite labile and by elimination of H 2 gives 10 . The molecular structure of 10 has been determined by X‐ray crystallography.