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'Phosphorylides' in keywords Facet   Publication Year 1988  [X]
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1988[X]
1Author    K. Endrich, P. Alburquerque, R. P. Korswagen, M. L. ZieglerRequires cookie*
 Title    Über die Reaktionen von Phosphoryliden mit homodinuklearen Organometallverbindungen des Molybdän und Wolfram On the Reaction of Phosphorylides with Homodinuclear Organometallic Compounds of Molybdenum and Tungsten  
 Abstract    We report first the complete study of the reactions of [CpMo(CO) 2 ]^ (Mo=Mo) (1, Cp = ?7 5 -C,H s) with salt-free phosphorus ylides Ph,P=CHR (2, Ph = QH,; R = H (2a), CH, (2b), C,H 7 (2c), C 6 H s (2d)) and with the Nal-adducts of the ylides Ph,P=CMe, (Me = CH,), PhMe 2 P=CH 2 and (PhO) 3 P=CH 2 . With 2, products of the type Cp(CO) 2 LMo-MoL(CO) 2 Cp (7, L = ylide) were obtained, and the salt adducts gave addition compounds of the type Cp(CO) 2 LMo-MoL(CO) 2 Cp-2NaI (12, L = ylide). These very reactive products represent novel bisphosphonioalkyl complexes, and were characterized by IR, mass and 'H NMR spec-trometry. The reaction of 1 with hexaphenylcarbodiphosphorane, C(PPh,) 2 , leads to a novel double addition product, Cp 2 Mo 2 (CO) 4 [C(PPh,) 2 ] 2 (14). Some reactions of compounds 7, 12 and 14 were also studied; 7d (L = CHPh —PPh,) reacts with NaNH 2 yielding ammonia and the disodium salt of the novel dianionic complex [CpMo(CO) 2 (CPh-PPh,)]^ 2 ~ (15); 7a (L = CH 2 —PPh,) reacts with CH,I forming CpMo(CO),CH, and traces of CpM~o(CO) 2 (PPh,)I; all compounds of types 7,12 and 14 react with adsorbents (Silica-gel, A1 2 0,, etc.); thus chromatogra-phy is impossible, even under strict protection from air and humidity. A study of the processes occurring during chromatography under various conditions and the resulting products are also reported and discussed. [CpW(CO),] 2 (18) reacts with 2 a forming also a bisphosphonioalkyl complex [CpW(CO) 2 L] 2 (L = CH 2 =PPh 3); in this case, the ylide substitutes two carbonyl groups in 18. The compounds [Cp*M(CO) 2 ] 2 (M^M) (Cp* = C 5 Me 5 ; M = Cr, W) apparently do not react with phosphorous ylides; the corresponding Mo compound, [Cp*Mo(CO) 2 ] 2 , does react, but only the new mono-nuclear complex Cp*Mo(CO) 2 (PPh,)Cl (22) could be isolated. 
  Reference    Z. Naturforsch. 43b, 1293—1306 (1988); eingegangen am 29. März/16. Juni 1988 
  Published    1988 
  Keywords    Phosphorylides, Homodinuclear Organometallic Compounds, Molybdenum, Tungsten 
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 TEI-XML for    default:Reihe_B/43/ZNB-1988-43b-1293.pdf 
 Identifier    ZNB-1988-43b-1293 
 Volume    43