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Synthesis, Structure and Reactivity of Trimethylsilyl‐Substituted Phosphametallocenes
Author(s) -
Loschen Rebekka,
Loschen Christoph,
Frank Walter,
Ganter Christian
Publication year - 2007
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.200600914
Subject(s) - chemistry , ruthenocene , reactivity (psychology) , trimethylsilyl , steric effects , electrophile , agostic interaction , ring (chemistry) , ligand (biochemistry) , denticity , nuclear magnetic resonance spectroscopy , stereochemistry , medicinal chemistry , crystallography , crystal structure , organic chemistry , metallocene , catalysis , medicine , biochemistry , alternative medicine , receptor , pathology , metal , polymerization , polymer
New sterically crowded phosphaferrocene and ‐ruthenocene derivatives were synthesized via the 2,5‐bis(trimethylsilyl)phospholide anion 5 . Their reactivity with regard to the exchange of the Me 3 Si groups for other functional groups was examined. X‐ray structures were determined for the mono‐ ( 6 ) and the 1,1′‐diphosphaferrocene ( 8 ). The activation barrier for ring–ring rotation in 8 was determined by NMR spectroscopy and supported by DFT calculations. Attempts to prepare 2,5‐difunctional phosphaferrocenes through electrophilic substitutions were unsuccessful, but yielded en route a new bidentate P,P ligand ( 3 ) and its Mo(CO) 4 complex, which were both characterized by X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)
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