The coordination chemistry of bidentate tellurium ligands. I. Complexes of palladium,platinum, and mercury with large chelate rings

Complexes formed from the reaction of palladium(II) and platinum(II) halides with (p-EtO·C₆H₄)Te(CH₂)_nTe(C₆H₄OEt-p) (Lⁿ, n = 6, 7, 8, 9, 10) are reported together with data for some mercury(II) complexes, [HgLⁿCl₂] which are used for comparative purposes. The compounds [MLⁿX₂] (M  Pd, Pt; n = 7, 8 (Pt only), 9, 10; X  Cl, Br) have molecular weights in molten naphthalene which fluctuate about the monomer value. [ML⁶X₂] (M  Pd, Pt; X  Cl, Br) are totally insoluble and are believed to be polymeric. The palladium(II) complexes have trans dichloro groups whereas the platinum compounds show cis dichloro groups in the solid state.¹³C NMR spectra are valuable to confirm the coordination of the ligand; the methylene resonance of the TeCH₂ group undergoes a 19–20 ppm downfield shift on coordination. ¹²⁵Te NMR spectra of the Pd(II) and Pt(II) complexes show two broad resonances the chemical shifts of which imply the presence of cis and trans isomers in CDCl₃ solution. A more detailed variable temperature high field study of [PtL⁸Cl₂] (¹²⁵Te and ¹⁹⁵Pt NMR) reveals a complex solution chemistry involving at least two cis and two trans species. The temperature range over which the solution is stable (−10 to 70 °C) is insufficient to allow a totally unambiguous interpretation but a model based on monomer ⇍ dimer equilibria provides a self consistent interpretation.     

The reactivity of bromoform with [Au(CH2)2PPh2]2. The completion of the halomethane series CHyX4−y (y=3,2,1,0; X=Cl,Br, I) and reactivity with [Au(CH2)2PPh2]2

The reaction of [Au(CH₂)₂PPh₂]₂ with excess CHBr₃ in benzene initially gives [Au(CH₂)₂PPh₂]₂₋ (CHBr₂)Br. This observation establishes that halomethanes, CH_yX_4−y (y=3,2,1,0; X=Cl, Br, I), react with [Au(CH₂)₂PPh₂]₂ to initially give Au(II) adducts of the general form [Au(CH₂)₂PPh₂]₂₋(CH_yX_3−y)X (y=3,2,1,0) via oxidative addition across the carbon-halogen bond. The order of reactivity inversely follows the order of carbon-halogen bond dissociation energies of haloalkanes. Methyl chloride is the only halomethane of the series that does not give a Au(II) adduct under similar reaction conditions.     

Interaction of tin methylchlorides SnMenCl4−n with molybdenum hydride bis(cyclopentadienyl)

The interaction between Cp₂MoH₂ (Cp=η⁵- C₅H₅) and SnMe_nCl_4−n (n=0−3) proceeds in aprotic solvent with the elimination of HCl and the formation of heterometallic complexes of the composition Cp₂Mo(H)SnMe_nCl_3−n (n=0−3) and Cp₂Mo(SnMe₂Cl)₂ which contains an MoSn σ-bond. It has been found that in all studied compounds the length of this bond is 0.20–0.30 Å less than the sum of the covalent radii of the Mo and Sn atoms.Based on analysis of the geometry of the Mo and Sn environment, the high values of the isomeric shifts (IS) in the Mössbauer spectra, the constants of the spin-spin interactions (SSI) J³_Cp-Sn and J²_HMoSn, and the considerably decreased values of the J²_Me-sn constants in ¹H NMR spectra, it was concluded that the decrease in the interatomic distance Mo-Sn is due to the high s-character of this bond. It is suggested that this effect, which is most pronounced in wedge-like complexes, is brought about by changing the orbital hybridization type of the tin atom from sp³ to s + 3p. This can explain the shorter interatomic distance M-Sn in heterometallic complexes of other types.     

Syntheses,characterization and redox properties of di- and poly-phosphine linked oligomeric complexes of oxo-centered triruthenium clusters

A series of phosphine-linked oligomers of oxo-centered triruthenium-acetate clusters have been prepared by the reaction of [Ru₃O(OAc)₆(py)₂(CH₃OH)](PF₆) (1) with di- or poly-phosphine. They have been characterized by elemental analysis, ESI-MS spectrometry, UV–Vis, IR, and ³¹P NMR spectroscopy, and cyclic and differential pulse voltammetry. The structures of diphosphine-linked dimeric compounds 4 and 7 were determined by X-ray crystallography. As revealed by redox wave splitting, weak to moderate electronic communication is operative between triruthenium clusters across bridging di- or poly-phosphine. With increase of the methylene number in Ph₂P(CH₂)_nPPh₂, electronic communication decreases rapidly in diphosphine-linked dimeric complexes [{Ru₃O(OAc)₆(py)₂}₂{μ-Ph₂P(CH₂)_nPPh₂}]²⁺ (n = 1–5).     

Effect of a phenyl group in quaternary ammonium compounds on thiamine uptake in isolated rat hepatocytes

The inhibitory effect of a phenyl group in quaternary ammonium compounds on thiamine uptake in isolated rat hepatocytes was investigated. The phenyltrimethylammonium ion was a more potent inhibitor than the tetramethylammonium ion, while the dibenzyldimethylammonium ion was the most potent inhibitor of thiamine uptake among those compounds examined. A kinetic study showed that this compound was a competitive inhibitor. The cetyltrimethylammonium ion was a less effective inhibitor than the benzyltrimethylammonium ion, and the palmitoylcholine ion was a weak inhibitor. These results indicate that the lipophilicity of a quaternary ammonium compound is not always correlated with its affinity for thiamine-carrier binding, but the presence of a phenyl group plays a significant role in affinity. The inhibitory effect of the series of (CH₃)₃N⁺(CH₂)_nC₆H₅ (n = 0−6) compounds on thiamine uptake in isolated rat hepatocytes was studied. The maximal inhibitory activity occurred at n = 5. These results suggest that the phenyl group in a quaternary ammonium compound has a specific interaction with the thiamine-binding site in rat liver plasma membrane.     

Organic derivatives of aluminium. Part I. Reactions of alkanolamines with aluminium isopropoxide

Reactions of alkanolamines [R₁R₂NXOH; R₁ = H, CH₃, C₂H₅; R₂ = H, CH₃, C₂H₅ and X = -CH₂CH₂-, -CH₂CH₂CH₂-, -CH₂CHCH₃, -C₆H₄CH₂CH₂-] with aluminium isopropoxide in different molar ratios (1 to 3) yield compounds of the type Al(OPrⁱ)_3?n(OXNR₁R₂)_n, where ‘n’ can be 1, 2 and 3. Most of the derivatives are distillable liquids, soluble in common organic solvents and susceptible to hydrolysis even by atmospheric moisture. The new derivatives are characterized by elemental analysis, IR and ¹H NMR spectra. Molecular weight measurements of Al(OPrⁱ)_3?n(OXNR₁R₂)_n reveal them to be tetrameric in nature.     

Coordinated 2-halo-l,3,2-dioxaphosphorinane ligands. I. syntheses and 13C, 17O, 31P and 95Mo NMR and IR spectroscopic characterization of some molybdenum pentacarbonyl complexes of 2-substituted-5, 5-dimethyl-1,3, 2-dioxaphosphorinanes

A study of the reactions of Mo(CO)₅(P(OCH₂- CMe₂CH₂0)X) (X = C1, Br) with a variety of nucleophiles of the type HER (E = NH, O, S; R = H, alkyl, aryl) is reported. The mechanism of these reactions is shown to be S_N2, and the significantly slower rates of reactions of n-propylamine with the above complexes relative to the rate of reaction of n-propylamine with Mo(CO)₅(Ph₂PC1) is discussed.The ¹³C, ¹⁷O, ³¹P and ⁹⁵Mo NMR data and infrared data for these complexes are presented. Good correlations between chemical shifts of the cis and trans CO¹³C and trans CO¹⁷0 NMR resonances, CO infrared stretching force constants and the magnitudes of ¹J_Mop and ²J_PC (trans CO) are observed and the reasons for these correlations are discussed.The correlations between the chemical shifts of NMR-active nuclei in the Mo(CO)₅(P(OCH₂CMe₂- CH₂O)ER) complexes with the chemical shifts of similar nuclei in the Mo(CO)₅(Ph₂PER) complexes fange from excellent to very poor. This indicates that the effects of-the P-substituents on the chemical shifts of the NMR-active nuclei in these complexes are not additive.     

Dicarboxylatodirhodium derivatives of polyoxotungstates

Salts of the new complexes [PW₁₁O₃₉{Rh₂(O₂CR)₂}]⁵⁻; R = Prⁿ (1), CH₂Cl (2), CH₂OH (3), o-C₆H₄OH (4), p-C₆H₄OH (5), and [XW₁₁O₃₉{Rh₂(p-O₂CC₆H₄OH)₂}]⁶⁻; X = Si (6), Ge (7) have been prepared in good yield and characterized by elemental analysis, multinuclear NMR spectroscopy, and structural crystallography of the cesium salts of anions 1 and 5 with chloride ions in axial positions of the dirhodium moiety. The incorporation of the dirhodium group into the Keggin structure significantly increases the hydrolytic kinetic stability of the polyoxotungstates at pH 7–8.5, a result that has implications for the use of such complexes for imaging and for phase determination in structural studies of large biomolecules. Based on NMR studies, the axial sites of the dirhodium moiety of the polytungstate anions are accessible to ligation by molecules such as cysteine, methionine, and isonicotinic acid.     

29Si and 13C chemical shifts and coupling constants of tris(phenyldimethylsilyl)methyl silicon compounds

Silicon-29 (δ ²⁹Si) NMR chemical shifts are reported for the first time for a number of tris(phenyldimethylsilyl)methyl silicon compounds (disilylated derivatives), (PhMe₂Si^A)₃C_αL, where LSi^BR₁R₂R₃, where R varies widely in electronegativity. δ ²⁹Si^B for these series exhibited to some extent good correlations with the electronegativities of the groups bonded to silicon (particularly, δ ²⁹Si^BMe₂X, X H, OH, OCH₃, COCH₃ and Cl). Substitution with electronegative atoms shifts the chemical shift of silicon to high field.The ¹³C NMR spectra of these compounds have been recorded and assigned. The chemical shifts of the α-carbon (C_α) resonances are shown to depend on the type of substituent on the silicon-B, thus ¹³C_α exhibit downfield shifts when X=oxygen ligand. The ¹³C phenyl resonances have been measured and show the same order of o, m and p signals, viz. δ ortho (downfield)>δ para>δ meta.The variation of ²⁹Si-¹H coupling constants with the electronegativity of X was studied.     

Resonance Raman spectroscopy of chemically modified retinals: Assigning the carbon-methyl vibrations in the resonance Raman spectrum of rhodopsin

To assign the observed vibrationsl modes in the resonance Raman spectrum of the retinylidene chromophore of rhodopsin, we have studied chemically modified retinals. The series of analogs investigated are the n-butyl retinals substituted at C₉ and C₁₃. The results obtained for the 11-cis isomer have clearly assigned the CCH₃ vibrational frequencies observed in the spectrum of the retinylidene chromophore. The data show that the C₍₉₎CH₃ stretching vibration can be assigned to the vibrational mode observed in the 1017 cm^?1 region, and the vibration detected at 997 cm^?1 can be assigned to the C₍₁₃CH₃ vibration. The C₍₅₎CH₃ stretching mode does not contribute to the vibrations observed in this region. The splitting in the C_(n)CH₃ (n = 9, 13) vibration is characteristic of the 11-cis conformation. The results on the modified retinals do not support the hypothesis that the splitting arises from equilibrium mixtures of 11-cis, 12-s-cis and 11-cis, 12-s-trans in solution. Thus, this splitting cannot be used to determine whether the chromophore in rhodopsin is in a 12-s-cis or 12-s-trans conformation. However, our results demonstrate that there are other vibrational modes in the spectra which are sensitive to this conformational equilibrium and we use the presence of a strong ~ 1271 cm^?1 mode in bovine and squid rhodopsin spectra as an indication that the chromophore in these pigments is 11-cis, 12-s-trans.     

Equilibrium constants under physiological conditions for the condensation of acetaldehyde with tetrahydrofolic acid

The nonenzymatic reaction of ethanol-derived CH₃CHO with tissue constituents continues to be of interest as a potential mechanism underlying the toxicity of alcohol. The current study has focused on the spontaneous condensation of CH₃CHO with H₄folate under physiological conditions (38 °C, pH 7.0, I = 0.25 M). Computer analysis of uv spectral changes with increasing CH₃CHO concentrations demonstrated the presence of at least two different adducts. The observed equilibrium constant (K_obs) for the formation of the first adduct is 91 ± 2 m^?1 (121 ± 2 m^?1 at 25 °C), a value which is unaffected by variations in ionic strength (0.06–1.0 m) or by free [Mg²⁺] up to 5 mm. The NMR spectrum is compatible with the structure: 5,10-CH₃CH-H₄folate analogous to the naturally occurring 5,10-CH₂-H₄folate. The formation of the latter compound from HCHO and H₄folate, however, is much more favorable under the same conditions [K_obs = 3.0 ± 0.2 × 10⁴ M^?1 (38 °C), 3.6 ± 0.1 × 10⁴ M^?1 (25 °C)]. At the levels of CH₃CHO which accumulate during ethanol metabolism in vivo only a small fraction of the H₄folate will exist as the CH₃CHO derivative, yet it may ultimately be the ratio of free CH₃CHO to free HCHO in tissue which determines the physiological importance of the CH₃CHO adduct. Other adduct(s) of CH₃CHO with H₄folate are observed at very high levels of CH₃CHO but are unlikely to be of physiological significance.     

Complexes of the fac-{Re(CO)3} core with tridentate ligands derived from arylpiperazines

Arylpiperazines, XC₆H₄N(CH₂CH₂)₂NH, are readily alkylated to give the N-alkylpiperazines of the type XC₆H₄N(CH₂CH₂)₂N(CH₂)_nNH₂. The amine functions of these derivatives are in turn easily subjected to mono- or dialkylation to provide potentially tridentate ligands of the types XC₆H₄N(CH₂CH₂)₂N(CH₂)_nN(H)(CH₂Y) and XC₆H₄N(CH₂CH₂)₂N(CH₂)_nN(CH₂Y)(CH₂Z), respectively. The latter class of dialkylated derivatives may be symmetrically (Y=Z) or unsymmetrically (Y ≠ Z) substituted. The donor groups Y and Z of this study include pyridine, imidazole, methyl-imidazole, thiazole, carboxylate and thiolate.The reactions of these ligands with [NEt₄]₂[Re(CO)₃Br₃] yield complexes of the type [Re(CO)₃{(YCH₂)N(H)(CH₂)_n(H)_xN(CH₂CH₂)₂N(H)_yC₆H₄X}]ⁿ and [Re(CO)₃{(ZCH₂)(YCH₂)N(CH₂)_n(H)_xN(CH₂CH₂)₂N(H)_yC₆H₄X}]ⁿ where the molecular charge n (0, +1, or +2) depends on the nature of the donor groups Y and Z (whether neutral or anionic or a combination of neutral and anionic) and on the degree of protonation of the piperazine unit (x=0 or 1; y=0 or 1). This variety of tridentate chelators provides complexes with fac-{Re(CO)₃N₃}, {Re(CO)₃N₂O}, {Re(CO)₃NO₂}, {Re(CO)₃N₂S} and {Re(CO)₃NS₂} coordination geometries. The structures of the model compound [Re(CO)₃{(CH₃N₂C₃H₂CH₂)N(H)CH₂CH₂-piperidine}]Br · H₂O, [Re(CO)₃{(CH₃N₂C₃H₂CH₂)N(H)CH₂CH₂-Fphenpip}]Br, [Re(CO)₃{(NC₅H₄CH₂)N(H)CH₂CH₂-Fphenpip}]Br, [Re(CO)₃{(O₂CCH₂)₂NCH₂CH₂CH₂-CH₃OphenpipH}] · xCH₃OH (x≈0.875), [Re(CO)₃{(NC₅H₄CH₂)₂NCH₂CH₂CH₂-CH₃OphenpipH}]Br₂ · 2CH₂Cl₂ · H₂O and [Re(CO)₃{(CH₃N₂C₃H₂CH₂)(O₂CCH₂)NCH₂CH₂CH₂-CH₃OphenpipH₂}]BrCl · 1.5CH₃OH · H₂O are discussed (phenpip: phenylpiperazine, -C₆H₄N(CH₂CH₂)₂N-).     

Metal Ion-Biomolecule Interactions. VIII: Methylmercury(II) Complexes of 8-Thioguanosine. Synthesis and Spectroscopic Investigations

The reaction of 8-thioguanosine (8-thioGuo^H₂ with methylmercury(II) has been shown to give rise to 1:1 (neutral and cationic), 1:2 (neutral and cationic), and 1:3 (cationic) complexes of the type [CH₃Hg(8-thioGuoH)], [(CH₃Hg(8-thioGuoH₂)]NO₃, [(CH₃Hg)₂(8-thioGuo)], [(CH₃Hg)₂(8-thioGuoH)]NO₃ and [(CH₃Hg)₃(8-thioGuo)]NO₃, depending upon the reactant stoichiometry and pH. ¹H NMR, ¹³C NMR, and IR, as well as analytical data were used to characterize the complexes. Coupling of methylmercury(II)-protons to mercury-199 has been observed in all compounds. The magnitude of the coupling, ²J(¹H-¹⁹⁹Hg), is strongly dependent on the nature of the ligand bonded to the methylmercury(II) group and correlates with the ¹³C chemical shifts of coordinated CH₃Hg(II) at the different binding sites.     

Organosilicon(IV) O,O-alkylenedithiophosphates

Tri- and di-organosilicon O,O-alkylenedithiophosphates, R_4−nSi[S₂PO₂G]_n (where R = Ph, Me, G = −C(CH₃)₂·C(CH₃)₂−, −CH₂C(CH₃)₂CH₂−, −CH-CH₃CH₂C(CH₃)₂−, n = 1,2) were synthesized by treatment of organosilicon(IV) chlorides with ammonium O,O-alkylenedithiophosphates in benzene. The compounds are volatile, yellow oily liquids, miscible with common organic solvents and monomeric in refluxing benzene. Like dialkyldithiophosphate derivatives of organosilicon(IV), these cyclic chain derivatives appear to be tetrahedral, the ligand behaving as unidentate.     

Effect of gem 2,2′-disubstitution and base in the formation of spiro- and ansa-1,3-propandioxy derivatives of cyclotriphosphazenes

The gem-dialkyl effect has been investigated in the reactions of cyclotriphosphazene, N₃P₃Cl₆1, with various 2,2′-derivatives of 1,3-propandiol, CXY(CH₂OH)₂, in either THF or DCM to form spiro (6-membered) and ansa (8-membered ring) derivatives. The reactions were made with a number of symmetrically-substituted (X = Y, methyl, ethyl, n-butyl and a malonate ester) and unsymmetrically-substituted (X ≠ Y, methyl/H, phenyl/H, methyl/n-propyl, ethyl/n-butyl and Br/NO₂) 1,3-propandiols. The products were analysed by ¹H and ³¹P NMR spectroscopy and some of the spiro and ansa derivatives were also characterized by X-ray crystallography. Reactions of 1 with unsymmetrically-substituted 1,3-propandiols results in the formation of two structural isomers of ansa-substituted compounds, both isomers (endo and exo) have been structurally-characterized by X-ray crystallography for the ethyl/n-butyl derivative. It is found that the regioselectivity of the reaction is changed when the base is changed. The relative proportions of spiro and ansa compounds formed under different reaction conditions were quantified by ³¹P NMR measurements of the reaction mixtures. The results were rationalised mainly in terms of the electronic effect of the substituents, whereas the steric effect has a secondary role in the formation of both spiro and ansa compounds.     

Oligophosphine ligands. XIII. Halo and hydro complexes of ruthenium(II) containing the novel tripod tetrakis(tertiary) phosphine P(CH2CH2CH2PMe2)3

The reaction of the ruthenium complexes RuCl₂(PPh₃)₃, RuCl₂(PPh₃)₄, RuCl₂(PMe₃)₄, RuCl₂(Me₂SO)₄, or RuBr₂(PPh₃)₃ with the tripod tetrakis(tertiary) phosphine P(CH₂CH₂CH₂PMe₂)₃ gave the compounds cis-RuCl₂ [P(CH₂CH₂CH₂PMe₂)₃] (1) and cis-RuBr₂[P(CH₂CH₂CH₂PMe₂)₃] (2). The coordination geometry of 1 and 2 was derived from the ABX₂ type ³¹P NMR patterns of the complexes, as well as from an X-ray structure determination for the chloride 1. Crystals of 1 were found to be monoclinic, space group P2₁/n (Z = 4), with a = 942.0(3), b = 1446.2(4), c = 1680(1) pm, and β = 104.99(4)°. Anisotropic refinement of the structure converged at R = 0.040 and R_w = 0.034 (3318 data). Selected bond lengths are (in pm): RuP(CH₂−)Me₂ (trans-atom P), 235.8(1) and 239.3(1); RuP(CH₂−)Me₂ (trans-atom Cl), 227.9(1); RuP(CH₂−)₃, 225.3(1); RuCl (trans-group P(CH₂−)₃), 252.1(1); and RuCl (trans-group P(CH₂)Me₂), 250.5(1). Reaction of 1 with LiAlH₄ yielded the hydro derivatives cis-Ru(H)Cl[P(CH₂CH₂CH₂PMe₂)₃] (3) and cis-RuH₂[P(CH₂CH₂CH₂PMe₂)₃] (4), which were characterized by IR and ¹H and ³¹p NMR spectroscopy.     

Group 3 complexes incorporating (furyl)-substituted disilazide ligands

A series of mono- and bis-amide scandium and yttrium compounds incorporating the furyl-substituted disilazide ligand, [N{SiMe₂R}₂]⁻ {i} (where R = 2-methylfuryl) have been synthesized. The compounds Sc{i}Cl₂ (1), Sc{i}(CH₂SiMe₃)₂ (2) and Sc{i}(OAr)₂ (3) were made from suitable scandium starting materials employing either a salt metathesis protocol with Li{i} or via protonolysis of Sc-C bonds by the neutral amine H{i}. The thermally unstable bis-alkyl yttrium compound, ‘Y{i}(CH₂SiMe₃)₂^’ was isolated as the bis-THF adduct (4) and the bis-aryloxide Y{i}(OAr)₂ (5) was synthesized by elimination of LiOAr from Y(OAr)₃. The bis-amide complex Y{i}₂Cl (6) and conversion to a rare example of an yttrium benzyl compound Y{i}₂(CH₂Ph) (7) are described. The yttrium cation, [Y{i}₂]⁺, was synthesized by benzyl abstraction from 7 using B(C₆F₅)₃. Structural characterization of representative examples show variation in the coordination modes for amide ligand {i}, differing primarily in the number of furyl groups that coordinate to the metal, with examples in which zero, one or two M-O_furyl bonds are present. Preliminary investigation in two areas of catalysis are presented.     

Chemical and structural aspects of cyclopentadienyl uranium(IV) tetrahydroborato complexes

Several new or partially described complexes of uranium(IV) of the series Cp _4−n U(BH ₄) _n [Cp=η ⁵- C ₅H ₅, η ⁵-C ₅H ₄CH ₃ or η ⁵-C ₅H ₄Si(CH ₃) ₃] are reported, mainly in order to systematically compare their physical, chemical and spectroscopic properties. X-ray data of the crystal structure of Cp ₃UBH ₄ are also reported.     

New synthesis of seven-coordinate complexes of molybdenum(II) and tungsten(II) containing bidentate phosphorus ligands, [MI2(CO)3{Ph2P(CH2)nPPh2}] (n = 1–6)

A new high yielding synthesis of the seven-coordinate complexes [MI₂(CO)₃{Ph₂P(CH₂)_nPPh₂}] (M = Mo and W; n = 1–6) is described. The procedure involves reacting the complexes [MI₂(CO)₃(NCMe)₂] in CH₂Cl₂ with an equimolar amount of the bidentate phosphorus ligand. The low temperature (−70 °C) ¹³C NMR spectra of the complexes [Wl₂(CO)₃{Ph₂P(CH₂)_nPPh₂}] (n = 3 and 5) indicates that the geometry is capped octahedral with a carbonyl ligand in the unique capping position.     

Synthesis, immobilization, and solid-state NMR of new phosphine linkers with long alkyl chains

Monodentate and chelating phosphines with long alkyl chains, incorporating ethoxy- or chlorosilane functions for immobilizations, have been synthesized and fully characterized. The new compounds (EtO)₃Si(CH₂)_xPPh₂, Cl₂Si(CH₂CH₂PPh₂)₂, and (EtO)₂Si[(CH₂)_xPPh₂]₂ (x = 7, 11) could be prepared in high yields from cheap starting materials, and they have been characterized by multinuclear NMR spectroscopy and X-ray crystallography. The phosphines have been immobilized on silica in a well-defined manner, and the modified silicas have been studied by ³¹P and ²⁹Si solid-state NMR of the dry materials and of the suspensions.