Reactivity of ortho‐Substituted Aryl–Palladium Complexes towards Carbodiimides,Isothiocyanates, Nitriles,and Cyanamides |
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| Authors: | José Vicente Prof?Dr José‐Antonio Abad Dr María‐José López‐Sáez Dr Peter?G Jones Prof?Dr Delia Bautista Dr |
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| Institution: | 1. Grupo de Química Organometálica, Departamento de Química Inorgánica, Facultad de Química, Universidad de Murcia, Aptdo. 4021, 30071 Murcia (Spain), Fax: (+34)?868‐884‐143 http://www.um.es/gqo/;2. Institut für Anorganische und Analytische Chemie, Technische Universit?t Braunschweig, Postfach 3329, 38023 Braunschweig (Germany);3. SAI, Universidad de Murcia, Apartado 4021, 30071 Murcia (Spain) |
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| Abstract: | Complexes Pd(C6H3XH‐2‐R′‐5)Y(N^N)] (X=O, NH; Y=Br, I; R′=H, NO2; N^N=N,N,N′,N′‐tetramethylethylenediamine (tmeda), 2,2′‐bipyridine (bpy), 4,4′‐di‐tert‐butyl‐2,2′‐bipyridine (dtbbpy)) react with RN?C?E (E=NR, S) or RC≡N (R=alkyl, aryl, NR′′2) and TlOTf (OTf=CF3SO3) to give, respectively, 1) products of the insertion of the C?E group into the C? Pd bond, protonation of the N atom, and coordination of X to Pd, Pd{κ2‐X,E‐(XC6H3{EC(NHR)}‐2‐R′‐4)}(N^N)]OTf or Pd(κ2‐X,N‐{ZC6H3(NH?CR)‐2‐R′‐4})(N^N)]OTf, or products of the coordination of carbodiimides and OH addition, Pd{κ2‐C,N‐(C6H4{OC(NR)}NHR‐2)}(bpy)]OTf; or 2) products of the insertion of the C≡N group to Pd and N‐protonation, Pd(κ2‐X,N‐{XC6H3(NH?CR)‐2‐R′‐4})(N^N)]OTf. |
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| Keywords: | carbodiimides insertion neighboring‐group effects N ligands palladium |
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