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Streubel, Rainer; Priemer, Siegfried; Ruthe, Frank; Jones, Peter G.; Gudat, Dietrich

doi:10.1002/(sici)1099-0682(199805)1998:5<575::aid-ejic575>3.3.co;2-l

Cited by 9 publications

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“…The outcome of the three-component reactions of the 2Hazaphosphirene complexes 1 a, 1 b, [11] and 1 c [12] with two equivalents of 1-piperidinonitrile and TCNE in toluene at 75 8C was surprising and depended significantly on the metal; complexes 1 a, b yielded no reaction products that could be identified or isolated. In the case of the tungsten complex 1 c, the D 5 -1,2-azaphospholene complex 2 c, a non-identified byproduct (d 163.9; < 5 %) and the 2H-1,4,2-diazaphosphole complex 3 c (< 5 %) were formed (Scheme 2); the reaction to WILEY-VCH Verlag GmbH, D- form 2 c represents the first example of a 1,3-dipolar cycloaddition of a nitrilium phosphane ylide complex to an alkene derivative.…”

Section: Resultsmentioning

confidence: 97%

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2000

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Competitive reactions of 2H-azaphosphirene metal complexes 1a-c (M =Cr, Mo, W) with 1-piperidinonitrile and tetracyanoethylene in toluene have been observed at elevated temperatures. For the case of complex 1c, the delta5-1,2-azaphospholene complex 2c (as main product) and the 2H-1,4,2-diazaphosphole complex 3c (as by-product) were separated from the product mixture. At ambient temperature and using 1-piperidinonitrile as solvent, bond and regioselective insertion of 1-piperidinonitrile into the P-N bond of 2H-azaphosphirene metal complexes 1a-c (M = Cr, Mo, W) has been achieved in the presence of tetracyanoethylene (TCNE), yielding 2H-1,4,2-diazaphosphole metal complexes 3a-c, analogous reactions in benzo- or acetonitrile afforded the 2H-1,4,2-diazaphosphole tungsten complexes 3d, e. A preliminary study with the 2H-azaphosphirene tungsten complex 1c and 1-piperidinonitrile as solvent has revealed that substoichiometric amounts of TCNE (0.3 equiv) induce approximately 70% conversion of complex 1c. NMR data of the complexes 2c and 3a-e and the X-ray structure of complex 3c are discussed.

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Section: Resultsmentioning

confidence: 97%

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2000

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“…The NMR spectra of 3a,b display characteristic 31 P resonances at about 100 ppm with tungsten-phosphorus coupling constant magnitudes of ca. 240 Hz.…”

Section: Resultsmentioning

confidence: 99%

Extended π conjugation in 2H-1,4,2-diazaphosphole complexes

et al. 2010

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“…Whereas complex 1a and phenylacetylene did not selectively react under these conditions, the C ‐thienyl‐substituted 2 H ‐azaphosphirene complex 1b 15 unexpectedly formed 2 H ‐1,2‐azaphosphole complex 3 (Scheme ) instead of a 3 H ‐1,3‐azaphosphole complex. Hence, instead of P–N‐bond‐selective ring enlargement, which was observed in reactions with nitriles,11 isonitriles (here) and carbonyl compounds,16 the P–C bond was selectively addressed in this case.…”

Section: Methodsmentioning

confidence: 96%

How To Tune Acid‐Induced Ring Enlargement Reactions – The Strange Case of 2H‐Azaphosphirene Complexes and Its Surprising Dichotomy

et al. 2009

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2H‐Azaphosphirene complex 1a reacted with TfOH, cyclohexyl isocyanide, and subsequently with NEt3 – P–N‐bond‐selectively – to give the first 2,3‐dihydro‐1,3‐azaphosphete complex 2. Under the same conditions, 2H‐azaphosphirene complex 1b underwent a P–C‐bond‐selective ring enlargement with phenylacetylene with formation of 2H‐1,2‐azaphosphole complex 3. Apart from X‐ray crystallographic data (2, 3), DFT calculations are discussed, which provide first insight into this surprising dichotomy.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Cited by 9 publications

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Extended π conjugation in 2H-1,4,2-diazaphosphole complexes

How To Tune Acid‐Induced Ring Enlargement Reactions – The Strange Case of 2H‐Azaphosphirene Complexes and Its Surprising Dichotomy

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