149754-22-3Relevant academic research and scientific papers
η1- und η2-Komplexe von Cp*-substituierten Diphosphenen und Arsaphosphenen: Synthese, Struktur und Umlagerung unter Cp*-Wanderung
Jutzi, Peter,Meyer, Udo,Opiela, Sylvia,Neumann, Beate,Stammler, Hans-Georg
, p. 279 - 301 (2007/10/02)
Metal complexes of the pentamethylcyclopentadienyl (Cp*)-substituted diphosphenes and arsaphosphenes 1-5 are described (Cp*P=PCp* (1), Cp*P=PAr (2), Cp*As=PAr (3), Cp*P=AsAr (4), Cp*P=AsCp* (5), Ar = 2,4,6-Tri-t-butylphenyl).In the reaction with metal carbonyls the trans-η1-complexes 6-12 are formed (Cp*(Mo(CO)5)P=PAr (6), Cp*(W(CO)5)P=PAr (7), Cp*(Cr(CO)5)P=PAr (8), Cp*(Cr(CO)5)As=PAr) (9), Cp*(Fe(CO)4)P=PAr (10), Cp*(Ni(CO)3)P=PAr (11), Cp*(Ni(CO)3)As=PAr (12)).The complexes 8,6,7 and 9 are converted photochemically to the cis-η1-complexes (13,14,15 and 16).The diphosphene 2 reacts with (Ph3P)Ni(C2H4)2 to yield the labile η1-complex Cp*(NiPPh3)P=PAr (24).The η2-complexes 17-21 are formed in the reaction of the corresponding diphosphenes or arsaphosphenes with (Ph3P)2Pt(C2H4) ((Ph3P)2Pt*1 (17), (Ph3P)2Pt*2 (18), (Ph3P)2Pt*3 (19), (Ph3P)2Pt*4 (20), (Ph3P)2Pt*5 (21)).In the reaction of 2 with (nBu3P)Ni(C2H4)2 the η2-complex (nBu3P)2Ni*2 (22) is formed as an intermediate; reaction with Ni(C2H4)3/TMEDA yields the labile η2-complex (TMEDA)Ni*2 (23).The η2-complex 22 and the η1-complex 24 rearrange easily to the corresponding nickela-diphosphenes 25 and 26 (Ph3P(Cp*)NiP=Ar (25), nBu3P(Cp*)*NiP=PAr (26)).These Cp* migration processes are discussed with respect to the underlying reaction sequences.The synthesis of the arsaphosphenes 4 and 5 is described.The structure of all new compounds is discussed on the basis of their 1H, 13C, and 31P NMR data.The complex 11 has been investigated also by X-ray crystallography.
