SUPPORTED ORGANOMETALLIC COMPLEXES .4. 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 = HCHCH2CH2O: R = (CH2)3Si(OCH3)3 (c), (CH2)3SiO3/2 (C')] with Cl2Pd(COD) (1) results in the formation of Cl2Pd(P approximately O)2 (3a-c). Cleavage of Cl- from 3 with AgSbF, yields the cationic, monochelated complexes [ClPd(P approximately O)(P and O)]+ (4a-c) (P approximately O: eta'-P-coordinated; P and O: eta2-O and P-coordinated). 4a crystallizes in the monoclinic space group P2(1)/c with the lattice constants a = 1062,4(2), b = 1912,2(4), and c = 1 635,5(3) pm, beta = 101,22(3)-degrees, and Z = 4 (R = 0,0341; R(w) = 0,033). With water 3b, c and 4b, c are subjected to polycondensation to give the supported complexes 3b', c', 4b', c'. The structure 3b', c', 4b', c' is investigated by comparison of their P-31 CP MAS data with the (P{H})-P-31-H-1 NMR spectra of their soluble precursors 3b, c, 4b, c. C-13 CP MAS NMR spectra of 3b', c' and 4b', c' indicate eta1-P- and eta2-O and P-coordination of the ligands. The polysiloxane network of 4b' was inspected by contact time variation of the Si-29 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.