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Study on the Ring Formation of 2 H ‐Azaphosphirene Complexes Using Sterically Demanding C ‐2,4,6‐Trialkylphenyl‐Substituted Aminocarbene Tungsten Complexes − Detection of a Key Intermediate
Author(s) -
Streubel Rainer,
Priemer Siegfried,
Ruthe Frank,
Jones Peter G.
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/(sici)1099-0682(200006)2000:6<1253::aid-ejic1253>3.0.co;2-i
Subject(s) - chemistry , carbene , steric effects , trimethylsilyl , methylene , adduct , triethylamine , medicinal chemistry , aryl , ring (chemistry) , reactivity (psychology) , alkoxy group , single crystal , stereochemistry , crystallography , alkyl , organic chemistry , catalysis , medicine , alternative medicine , pathology
The synthesis of C ‐2,4,6‐trialkylphenyl‐substituted ethoxy‐ and aminocarbene tungsten complexes 1a−c (R = Me, i Pr and t Bu) and 2a,b (R = Me, i Pr) and the reaction of 2a,b with [bis(trimethylsilyl)methylene]chlorophosphane ( 3 ) in the presence of triethylamine is reported. The reaction course, which finally leads to the 2 H ‐azaphosphirene complexes 7a,b , depends strictly on the steric demands of the aryl group bonded to the carbene atom; only in the case of complex 2a was a dinuclear tungsten carbene complex formed, which was isolated and characterized by single crystal X‐ray diffraction. Relative to phenyl‐substituted derivatives, the 2 H ‐azaphosphirene complexes 7a,b showed enhanced reactivity towards triethylammonium chloride, furnishing the [bis(trimethylsilyl)methyl]chlorophosphane complex 8 . Condensation of 8 with complex 2a afforded the novel dinuclear tungsten complex 9a containing an acyclic C,N,P structural unit with a κ‐C and a κ‐P coordination mode; an H‐bonded adduct of complex 9a and mesitylnitrile, complex 10 , was investigated by single crystal X‐ray diffraction.