Abstract: | 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)3SiO3/2 ( b ′); D= R=(CH2)3Si(OCH3)3 ( c ), (CH2)3SiO3/2 ( 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; Rw=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. |