Trägerfixierte Organometallkomplexe. IV. Strukturuntersuchungen an neutralen und kationischen (Ether-phosphan)palladium(II)-Komplexen

Supported Organometallic Complexes. IV. Structural Investigations on Neutral and Cationic (Ether-phosphane)palladium(II) Complexes . Reaction of the (ether-phosphane) ligands PhP(R)CH₂—D ( 2a?c ) [D=CH₂OCH₃: R=Ph ( a ), (CH₂)₃Si(OCH₃)₃ ( b ), (CH₂)₃SiO_3/2 ( b ′); D= R=(CH₂)₃Si(OCH₃)₃ ( c ), (CH₂)₃SiO_3/2 ( c ′)] with Cl₂Pd(COD) ( 1 ) results in the formation of Cl₂Pd(P — O)₂ ( 3a?c ). Cleavage of Cl^? from 3 with AgSbF₆ yields the cationic, monochelated complexes [ClPd(P — O)(P ∩ O)]⁺ ( 4 a—c ) (P — O: η¹-P-coordinated; P ∩ O: η²-O ∩ P-coordinated). 4 a crystallizes in the monoclinic space group P2₁/c with the lattice constants a=1 062,4(2), b=1 912,2(4) und c=1 635,5(3) pm, β=101,22(3)° and Z=4 (R=0,0341; R_w=0,033). With water 3 b, c and 4 b, c are subjected to polycondensation to give the supported complexes 3 b′, c′, 4 b′, c ′. The structure 3 b′, c′, 4 b′, c ′ is investigated by comparison of their ³¹P CP MAS data with the ³¹P{¹H} NMR spectra of their soluble precursors 3 b, c, 4 b, c . ¹³C CP MAS NMR spectra of 3 b′, c ′ and 4 b′, c ′ indicate η¹-P- and η²-O ∩ P-coordination of the ligands. The polysiloxane network of 4 b ′ was inspected by contact time variation of the ²⁹Si CP MAS NMR spectra and it appeared that 77% of the Si—O units are crosslinked, corresponding to a ratio T₄:T₃:T₁=67:100:10.