Solid-State (31)P NMR studies reveal that phosphinine ligands employed for the stabilisation of gold nanoparticles react in part during the synthesis, and that the particles are stabilised by a mixture of intact phosphinine units together with several other surface-bound species. The spectral data of these species are characteristic for phosphine-type donors although unambiguous structure assignment was as yet unfeasible. The spectral data of surface-bound phosphinines were verified by comparison with the spectrum of an authentic complex [()AuCl]. The metal-bound phosphinines in both the complex and the nanoparticles prefer eta(1)(P)-coordination to a single metal atom, and the observation of splittings arising from coupling with (197)Au (I = 3/2) nuclei indicates that these ligands are not mobile. The fraction of intact phosphinines on the nanoparticles drops with decreasing steric protection although the observed product distribution shows no simple relation with substituent patterns.

Phosphinines with pendant phenol or catechol functionalities and their gold(I) complexes were synthesised and characterised by spectroscopic data and in one case by a single-crystal X-ray diffraction study. Reactions of ligands or complexes with TiO 2 or chloropropyl modified hexagonal mesoporous silica were then studied with the aim to immobilise ligands or complexes on the carrier by covalent tethering. 31 P MAS NMR studies revealed that immobilisation on TiO 2 www.zaac.wiley-vch.de 1359 3a: from 1a (100 mg, 0.28 mmol) and AuCl(tht) (90 mg, 0.28 mmol). Yield: 150 mg (91 %); m.p. 202°C. C 23 H 17 O 2 P 1 Cl 1 Au 1 (588.78): calcd. C 46.92, H 2.91; found C 47.84, H 3.53. 31 P{ 1 H} NMR (CD 2 Cl 2 ): δ = 152.40. 1 H NMR (CD 2 Cl 2 ): δ = 6.88 (dd, 3 J HH = 0.8, 4 J HP = 8.2 Hz, 1 H), 7.18 (dt, 4 J HH = 2.2, 3 J HP = 8.1 Hz, 1 H), 7.28-7.35 (m, 1 H), 7.41-7.57 (m, 6 H), 7.77-7.88 (m, 4 H), 8.44 (dd, 4 J HH = 1.6, 3 J HP = 22.4 Hz, 1 H, H at C3/C5), 8.52 (dd, 4 J HH = 1.6, 3 J HP = 22.4 Hz, 1 H, H at C3/C5).

Two isomeric bis(phosphane) palladium chloride complexes with functional catechol phosphane ligands were immobilised on different specimens of TiO 2 . The solid materials were characterised by 31 P NMR spectroscopy both when dry and as suspensions in various solvents. The NMR spectroscopic studies demonstrated that the resistance towards leaching varies strongly with the nature of the carrier material and

Reactions of 2-formyl-3,4-dimethyl-1-phosphaferrocene with aminopropyl (AP) functionalized hexagonal mesoporous silica (HMS) were studied in the absence and presence of an excess of the mild reducing agent Na[BH 3 CN]. Starting material and reaction products were characterized by analytical and multinuclear ( 13 C, 29 Si, 31 P) MAS NMR spectroscopic data. Both reactions proceeded by partial derivatization of surface-bound NH 2 groups to yield products with tethered phosphaferrocene units. Evaluation of spectroscopic data and the results of homogeneous model reactions confirmed that condensa-

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