Übergangsmetallphosphidokomplexe. XV. (DRPE)Ni-Komplexe mit PH-haltigen η2-koordinierten Diphosphenliganden und die Diphosphorkomplexe [(DRPE)Ni]2P2

Transition Metal Phosphido Complexes. XV. (DRPE)Ni-Complexes with PH-Containing, η²-Coordinated Diphosphene Ligands and the Diphosphorus Complexes (DRPE)Ni]₂P₂ The complexes (DRPE)NiCl₂ 1 (DRPE = R₂PCH₂CH₂PR₂; R = Et: DEPE a ; R = Cy: DCPE b ; R = Ph: DPPE c ) react with the silylphosphines (Me₃Si)₃P, (Me₃Si)₂PH, Me₃SiPH₂ and (Me₃Si)₂P]₂ to form the diphosphorus complexes (DRPE)Ni]₂P₂ 3a–c and the nickel(0) complexes (DRPE)₂Ni 4a–c . In the reaction of 1b with Me₃SiPH₂ the P₂H₂ complex (DCPE)Niη²-(PH)₂] 5b can be isolated at low temperature as an intermediate. Cleaving the Si? P bonds in (DRPE)Niη²-(PSiMe₃)₂] 2a, 2b with CH₃OH gives also the P₂ complexes 3a, 3b . Intermediates containing HP=PSiMe₃ and P₂H₂ as ligands can be detected nmr spectroscopically. Reacting 1a–c with (Me₃Si)₂PP(SiMe₃)CMe₃ the complexes (DRPE)Ni(η²-Me₃SiP?PCMe₃) 7a–c containing asymmetric diphosphene ligands can be obtained. 7a reacts with CH₃OH yielding the P₂ complex 3a directly, while 7b with CH₃OH first gives (DCPE)Ni(η²-HP?PCMe₃) 8b . In solution 8b can be transformed into 3b upon heating to 80°C. N.m.r. and mass spectral data are reported.