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A polymer-protected palladium colloid (Pd/PVP, PVP = poly-N-vinylpyrrolidone) has been used to catalyze H−D exchange between the D2O solvent and pyridine, substituted pyridines, and related N-heterocycles. Within a few hours under ambient conditions, significant exchange at the positions adjacent (α) to the endocyclic nitrogen was observed for 4-dimethylaminopyridine, 4-methoxypyridine, 4-methylpyridine, pyridine, and quinoline. H−D exchange was observed also for the methyl group in 4-methylpyridine and for the fused-ring H8 position in quinoline. N-Methylimidazole was rapidly and selectively deuterated at the H2 position. Nonselective deuteration was observed at various ring positions (but not the methyl group) for 3-methylpyridine. The presence of a β substituent in 3-cyanopyridine and nicotinic acid hindered H−D exchange at the adjacent α (H2) site, but significant deuteration was observed for the second α position (H6). Portions of the 2- and 4-vinylpyridine samples underwent rapid hydrogenation to 2-...

The organometallic osmium(VI) hydroxo compounds [N(n-Bu)4][Os(N)(CH2SiMe3)3(OH)], cis and trans isomers of [N(n-Bu)4][Os(N)(CH2SiMe3)2(OH)2], result from the substitution of chloride for hydroxide ligands in precursor compounds. Depending on the molecular structure, these compounds behave as nucleophiles, Bronsted bases, or Lewis bases in their reactions. One of these, [N(n-Bu)4][cis-Os(N)(CH2SiMe3)2(OH)2], reacts readily with CO2 to produce the carbonate compound [N(n-Bu)4][Os(N)(CH2SiMe3)2(CO3)]. The other isomer, [N(n-Bu)4][trans-Os(N)(CH2SiMe3)2(OH)2], reacts with CO2 to slowly form the same carbonate compound. It is protonated by other acids to give the neutral hydroxo dimer {Os(N)(CH2SiMe3)2(μ-OH)}2. The anti isomer of {Os(N)(CH2SiMe3)2(μ-OH)}2 reacts with Pd(bpy)(OSiMe3)2 to produce the coordinatively unsaturated, heterometallic complex {Os(N)(CH2SiMe3)2}2(μ3-O)2Pd(bpy). The molecular structure of this complex shows two square-pyramidal osmium groups with an anti arrangement of the apical nitrido l...

Protonation of Os(η5-C5H5)(N)(CH2SiMe3)2 with either HBF4 or CF3SO3H at low temperature produces a thermally unstable imido complex, [Os(η5-C5H5)(NH)(CH2SiMe3)2][X] (X = BF4, SO3CF3). The imido com...

The reaction between Ni(dppe)(SSiMe3)2 and 2 equiv of [N(n-Bu)4][Ru(N)Cl2Me2] produces ClSiMe3 and the heterometallic complex (dppe)Ni(μ3-S)2{Ru(N)Me2}2. The molecular structure of this complex shows the three metals and the two nitrido ligands in a plane with the bridging sulfur atoms above and below that plane. There is an interaction between one of the ruthenium centers and the nickel. The structure differs from that of the closely related complex (dppe)Pt(μ3-S)2{Ru(N)Me2}2, which has equivalent Pt−Ru distances and no strong metal−metal interactions. The complexes (dppe)M(μ3-S)2{Ru(N)Me2}2 (M = Pt, Pd, Ni) catalyze the oxidation of benzyl alcohol to benzaldehyde in toluene and in supercritical carbon dioxide.

The chiral-at-metal osmium complex [N(n-Bu)4][cis-Os(N)(CH2SiMe3)PhCl2] results from series of alkylation and protonation reactions from [N(n-Bu)4][Os(N)Cl4]. (S,S)-Chiraphos displaces a chloride from this complex to produce two isomers of Os(N)(CH2SiMe3)PhCl((S,S)-chiraphos) with different configurations at osmium. 31P NMR spectroscopy indicates that one isomer has a phosphorus donor from the chiraphos ligand trans to the nitride, while the other has chloride in this position. Molecular mechanics calculations suggest that the axial phosphine isomer has an S configuration at osmium. This isomer reversibly loses an additional chloride ion and can be separated from the isomer with the opposite configuration by the careful addition of AgSbF6. The diastereomers [SbF6][(S)-Os(N)(CH2SiMe3)Ph((S,S)-chiraphos)] and [SbF6][(R)-Os(N)(CH2SiMe3)Ph((S,S)-chiraphos)] can be isolated separately. The two isomers of [SbF6][Os(N)(CH2SiMe3)Ph((R,R)-chiraphos)] are enantiomers to those of [SbF6][Os(N)(CH2SiMe3)Ph((S,S)-chira...

The cluster Ir 3 (CO) 3 (η 5 -C 9 H 7 ) 3 (1) reacts with HBF 4 .Et 2 O to form [Ir 3 (μ-H)(CO) 3 (η 5 -C 9 H 7 ) 3 ]-[BF 4 ] (2). Deprotonation of 2 with NEt 3 generates C s -Ir 3 (CO) 3 (η 5 -C 9 H 7 ) 3 (1c), which rapidly reverts to an equilibrium mixture containing C 3 v -Ir 3 (μ-CO) 3 (η 5 -C 9 H 7 ) 3 (la) as the major isomer. Activation parameters for the reversion are ΔH = 17.0(3) kcal mol - 1 and ΔS = -13(1) cal mol - 1 K - 1 , and K e q = [1a]/[1c] = 16.7(7) at 25 °C. Variable-temperature NMR experiments indicate that 1c undergoes a dynamic process, with T c = -30 °C and ΔG c = 12.4(3) kcal mol - 1 , which equilibrates the three indenyl ligands but does not equilibrate the two sets of CO ligands on opposite sides of the Ir 3 plane.

Treatment of dilithiated 1,2-bis(3-indenyl)ethane with M(CO)5(THF) (M = Mo, W) followed by oxidation provided the metal−metal bonded compounds M2(CO)6{μ-(η5-C9H6)2C2H4} (1, M = W; 2, M = Mo) as a m...

The electrochemical behavior of the face-coordinated C 6 0 -carbidopentaruthenium cluster complexes Ru 5 C(CO) 1 1 (PPh 3 )(μ 3 -η 2 ,η 2 ,η 2 -C 6 0 ) (1), Ru 5 C(CO) 1 0 (μ-η 1 ,η 1 -dppf)(μ 3 -η 2 ,η 2 ,η 2 -C 6 0 ) (2) (dppf = 1,1'-bis(diphenylphosphino)ferrocene), and PtRu 5 C(CO) 1 1 (η 2 -dppe)μ 3 -η 2 ,η 2 ,η 2 -C 6 0 ) (3) (dppe = 1,2-bis(diphenylphosphino)ethane) has been examined by cyclic voltammetry, rotating disk electrode voltammetry, and differential pulse voltammetry methods. The behavior of compounds Ru 5 C(CO) 1 5 (4), Ru 5 C(CO) 1 4 (PPh 3 ) (5), Ru 5 C(CO) 1 3 (μ-η 1 ,η 1 -dppf) (6), PtRu 5 C(CO) 1 6 (7), and PtRu 5 C(CO) 1 4 (η 2 -dppe) (8) was studied also for comparison. For both 1 and 3, the voltammetric scans show an initial irreversible two-electron reduction feature, followed by three quasi-reversible, one-electron reductions of the C 6 0 ligand. In contrast, similar scans for 2 indicate an initial quasi-reversible, one-electron reduction of the C 6 0 ligand that is dynamically coupled with a second one-electron, irreversible reduction. Stepwise reduction of the C 6 0 ligand proceeds at more negative potentials. Interpretation of the electrochemical behavior of compounds 1-8 has been enhanced by studying their chemical reduction with cobaltocene. In all cases uptake of two electrons results in irreversible loss of a CO ligand from the cluster, and the resulting dianionic complexes have been characterized by their IR (ν C O ) spectra.

The trimethylsilanethiolate complexes of the platinum triad metals (dppe)M(SSiMe3)2 (M = Ni, Pd, Pt) and (COD)Pt(SSiMe3)2 were prepared by the reaction of NaSSiMe3 with (dppe)MCl2 or (COD)PtI2. The...

Heating a mixture of M2(CO)10 (M = Re, Mn) with 1,2-bis(indenyl)ethane in Decalin at ca. 180 °C provided both monometalated M(CO)3{(η5-C9H6)C2H4C9H7)} (1, M = Re; 3, M = Mn) and bimetalated (M(CO)3)2{μ-(η5-C9H6)C2H4(η5-C9H6)} (2, M = Re; 4, M = Mn) products, which were separated by chromatography, isolated as pure solids, and characterized by a combination of analytical and spectroscopic methods. The bimetalated compounds 2 and 4 were formed as a mixture of meso and rac diastereomers; the rac form of 2 crystallized selectively, and its structure was determined by X-ray crystallography. UV photolysis of 1 and 3 (or 4) yielded the compounds M(CO)2{(η5-C9H6)C2H4(η2-C9H7)} (5, M = Re; 6, M = Mn), in which a carbonyl ligand is replaced by the η2 coordination of the pendant indene group. UV photolysis of 2 gave primarily the rearranged isomer Re2(CO)6{μ-(η1:η2-C9H6)C2H4(η5-C9H6)} (7), in which one indenyl group bridges the two Re centers as an η1:η2-vinyl moiety. The molecular structures of compounds 6 and 7 al...

Treatment of the phosphine ligand derivatives (μ-H)2Os3(CO)9L (L = PEt3, PEt2Ph, PPh3, PiPrPh2, PCy3) with excess ethereal diazomethane at −78 °C provides a set of compounds with the formula Os3(CO)9L(“CH4”). As isolated solids these compounds exist as methylene ligand complexes, and the structure of (μ-H)2Os3(CO)9(PPh3)(μ-CH2) has been determined by single-crystal X-ray crystallography. A triangular array of osmium atoms supports a methylene moiety bridging one Os−Os vector, and the triphenylphosphine ligand is bound to the remaining osmium center in an "in-plane” position. The hydride ligands have been located and refined; one also bridges the same edge as the methylene ligand, and the other forms a single bridge in a position cis to the phosphine ligand. Analysis of the solution 1H and 13C NMR spectra of (μ-H)2Os3(CO)9(PPh3)(μ-CH2) indicates that the solid-state structure is maintained in solution. However, also present in solution is a methyl tautomer, (μ-H)Os3(CO)9(PPh3)(μ-CH3), the structure of whic...

The substitution of carbonyl ligands in the edge-shared bioctahedral cluster [PPN]2[Ru10C2(CO)24] by two types of 4e donor π-bonding ligands, viz., a diene (norbornadiene) and an alkyne (diphenylac...

Substitution of carbonyl ligands in [Ru10C2(CO)24]2- (1) by allene (1,2-propadiene) proceeds cleanly in diglyme at 90 °C (1 atm) to afford the monoallene derivative [Ru10C2(CO)22(μ-η2:η2-C3H4)]2- (2). Treatment of either 1 or 2 with allene at 140 °C (1 atm) forms the disubstituted derivative [Ru10C2(CO)20(μ-η2:η2-C3H4)2]2- (3) in high yield. The new clusters have been isolated as salts with [PPN]+ or [PPh3CH2CH2PPh3]2+ counterions and have been characterized by analytical, spectroscopic, and X-ray crystallographic methods. The framework structures of both molecular cluster anions 2 and 3 are based on edge-shared bioctahedra, with the allene ligands bridging one or two pairs of apical positions, respectively. The idealized symmetries are C2 for 2 and D2 for 3. The solution structures and dynamics of 2 and 3 have been studied by 13C NMR spectroscopy, including variable-temperature and 13C−13C COSY experiments.

Oxidative substitution of [Ru10C2(CO)22(NBD)]2- with ferrocenium ion and diazomethane forms a methylene compound, Ru10C2(CO)22(NBD)(μ-CH2), in which the methylene ligand symmetrically bridges two adjacent apical ruthenium centers in the edge-fused bioctahedral Ru10C2 framework. A methylidyne tautomer, Ru10C2(CO)22(NBD)(CH)(H), is formed reversibly at 80 °C.

Interaction of Ru5C(CO)15 with C60 in refluxing chlorobenzene followed by PPh3 or dppe (1,2-bis(diphenylphosphino)ethane) forms Ru5C(CO)11(PPh3)(μ3-η2,η2,η2-C60) (1) or Ru5C(CO)10(μ-η1,η1-dppe)(μ3-η2,η2,η2-C60) (2), isolated in 19% and 14% yields, respectively, after chromatography. An analogous reaction of Ru5C(CO)15 with C60 followed by dppf (1,1‘-bis(diphenylphosphino)ferrocene) initially forms both Ru5C(CO)11(η1-dppf)(μ3-η2,η2,η2-C60) (3) and Ru5C(CO)10(μ-η1,η1-dppf)(μ3-η2,η2,η2-C60) (4), but further thermolysis of 3 in refluxing chlorobenzene converts it to 4. Direct interaction of Ru5C(CO)14(PPh3) (5), Ru5C(CO)13(dppe) (6), and Ru5C(CO)13(dppf) (7) with C60 in refluxing chlorobenzene also provides 1, 2, and 4 in isolated yields of 21%, 27%, and 20%, respectively. Interaction of PtRu5C(CO)16 or PtRu5C(CO)14(COD) with C60 followed by dppe in refluxing chlorobenzene forms PtRu5C(CO)11(η2-dppe)(μ3-η2,η2,η2-C60) (8) (7% and 23% yields, respectively). Substitution of the COD ligand in PtRu5C(CO)14(COD) by...

The photolysis of M(CO)4(dppe) (M = Mo, W) and C60, C70, or dimethyl fumarate (dmf) in chlorobenzene provides M(CO)3(dppe)(η2-C60) (M = Mo, 1; M = W, 2), Mo(CO)3(dppe)(η2-C70) (3), and W(CO)3(dppe)...

Oxidation of the decaruthenium carbonyl cluster [Z]2[Ru10C2(CO)24] (1) (Z+ = PPN+, Et4N+) with [Cp2Fe][BF4] (2 equiv) at room temperature in the presence of disubstituted alkynes forms the neutral derivatives Ru10C2(CO)23(C2RR‘) (2, R, R‘ = Ph2; 3, R, R‘ = Tol2; 4, R, R‘ = Ph, Me). Compounds 2−4 are readily reduced with methanolic hydroxide to produce the previously known [Ru10C2(CO)22(C2Ph2)]2- (5) and its analogs.

The reaction of Ir(CO)(η2-C8H14)(η5-C9H7) with excess C2R2 (R = Ph, Tol) in benzene at reflux leads to a mixture containing Ir(CO)(η2-C2R2)(η5-C9H7) (1a, R = Ph; 1b, R = Tol), Ir2(CO)2(μ-C2R2)(η5-C9H7)2 (2a, R = Ph; 2b, R = Tol), and Ir(η4-HC4R4R‘)(η5-C9H7) (3a, R = Ph, R‘ = Ph; 3b, R = Tol, R‘ = Ph). Conducting the reaction in benzene-d6, toluene, or m-xylene leads to 1 and 2 and Ir(η4-DC4R4R‘)(η5-C9H7) (3c, R = Tol, R‘ = C6D5) or Ir(η4-HC4R4R‘)(η5-C9H7) (3d, R = Ph, R‘ = C6H4Me; 3e, R = Ph, R‘ = C6H3Me2; 3f, R = Tol, R‘ = C6H4Me). The structures of compounds 2a and 3b have been determined by X-ray diffraction. Compound 2a contains a dimetallacyclobutene framework with the CO ligands adopting a trans orientation with respect to the Ir2C2 mean plane. The indenyl ligands take positions opposite the carbonyls at each Ir center. Compound 3b contains a 1-phenyl-1,2,3,4-tetratolyl-1,3-butadiene ligand formed through both alkyne coupling and CH bond activation of the solvent benzene. The direct reactions of 1 w...

Osmium(VI) complexes with cyclopentadienyl, indenyl, and hydrotris(3,5-dimethylpyrazolyl)borate ligands result from the reaction between [Os(N)Ph2(py)2][BF4] and sodium cyclopentadienide, potassium indenide, or potassium hydrotris(3,5-dimethylpyrazolyl)borate. The molecular structures of the resulting complexes, CpOs(N)Ph2 (1), InOs(N)Ph2 (2), and Tp*Os(N)Ph2 (3), have been determined by X-ray diffraction analysis. The cyclopentadienyl-type ligand in each complex is distorted due to the strong trans effect of the nitrido group.

The reactions of C3v Ir3(μ-CO)3(η5-C9H7)3 (1) with various metal electrophiles yield the cationic tetranuclear clusters [Ir3{M(PPh3)}(CO)3(η5-C9H7)3][PF6] (2, M = Cu; 3, M = Ag; 5, M = Au), [Ir3Tl(μ-CO)3(η5-C9H7)3][PF6] (4), and [Ir3(HgR)(CO)3(η5-C9H7)3][PF6] (6, R = Ph; 7, R = W(CO)3(η5-C5H5)). Compounds 5−7 are best prepared via compound 4. The structures of compounds 4 and 5 have been determined by X-ray diffraction. The C3v symmetry of the parent cluster 1 is maintained in the structure of 4. The molecule consists of a triangle of iridium atoms, each edge of which has a bridging carbonyl oriented out of the plane in the same direction and each vertex of which has an η5-indenyl ligand oriented toward the opposite side of the plane. The thallium atom adopts a face-capping mode of coordination on the same side of the triiridium plane as the three indenyl ligands and is encapsulated by the phenylene portions of the indenyl groups. The molecular structure of 5 consists of a AuIr3 butterfly framework with a...

Primary, secondary, and tertiary alkanethiolate complexes of osmium(VI) possessing bridging thiolate ligands have been prepared and characterized. The complexes [Os(N)(CH2SiMe3)2(μ-SR)]2 (R = CH2CH3, CMe3, CHMe2, CH2CHMe2, CH2Ph) are synthesized by the reaction of [Os(N)(CH2SiMe3)2Cl]2 with alkali metal thiolates. They are air- and water-stable and unreactive toward nucleophiles and electrophiles. Anionic tetrathiolate and tetraalkoxide complexes of osmium(VI) have also been prepared and characterized. Reaction of [PPh4][Os(N)Cl4] with NaSCH2Ph or LiOCH2Ph in refluxing THF produces [PPh4][Os(N)(SCH2Ph)4] or [PPh4][Os(N)(OCH2Ph)4]. Thermolysis of [PPh4][Os(N)(SCH2Ph)4] gives benzyl disulfide, probably via reductive elimination, while the tetraalkoxide complex produces benzaldehyde and benzyl alcohol upon heating in a β-hydrogen elimination reaction.

As reported previously by Brown and Evans, the reaction of (μ-H)2Os3(CO)9(PPh3) with acetylene provides two isomers of the hydrido vinyl compound (μ-H)Os3(CO)9(PPh3)(μ-η2-CHCH2) (2). The solid-state structures of these two isomers now have been defined by single-crystal X-ray crystallography. The major isomer 2a contains a triangular array of osmium atoms with the vinyl ligand bridging the Os(2)−Os(3) edge, forming a σ-bond to Os(3) and a π-bond to Os(2), and the triphenylphosphine ligand coordinating to Os(2) in an “in-plane” position. The presence of the hydride ligand also bridging the Os(2)−Os(3) edge was deduced indirectly. The minor isomer 2b also contains a triangular Os3 array with the vinyl ligand bridging the Os(2)−Os(3) edge and forming a σ-bond to Os(2) and a π-bond to Os(3). The triphenylphosphine ligand is bound to Os(1). The presence of the bridging hydride on the Os(1)−Os(3) edge was not directly detected but was supported by analysis of the structure; the hydride ligand therefore does not...

The imido ligand in [(η5-C5H5)Os(NCH3)(CH2SiMe3)2][SO3CF3] reacts with basic and nucleophilic molecules. Triphenylphosphine, pyridine, and water act as bases and deprotonate the methylimido ligand forming the first osmium(IV) methyleneamido complex, (η5-C5H5)Os(NCH2)(CH2SiMe3)2. The reaction is reversible, and treatment of (η5-C5H5)Os(NCH2)(CH2SiMe3)2 with HBF4 produces [(η5-C5H5)Os(NCH3)(CH2SiMe3)2][BF4]. Triphenylphosphine also abstracts the imido ligand to form MeNPPh3. The imido complex reacts with ethylene to produce an olefin complex, [(η5-C5H5)Os(NHCH2)(CH2CH2)2][SO3CF3]. Under pressures of ethylene, products resulting from imide transfer to the olefin are obtained.

The complex CpIr(η 4 -C 5 H 6 ) was prepared unexpectedly from the reaction of [(η 2 -C 8 H 14 ) 2 IrCl] 2 and thallium cyclopentadienide

The first cyclopentadienyl-nitrido complexes of a transition metal were prepared by the reactions between [NBu n 4 ][Os(N)Cl 2 (CH 2 SiMe 3 ) 2 ] and either NaC 5 H 5 or LiC 5 Me 5 . They are soluble in organic solvents, volatile, and stable to air and water. The nitrogen atom in (η 5 -C 5 H 5 )Os(N)(CH 2 SiMe 3 ) is a «soft» Lewis base. It binds reversibly to BF 3 in solution, forming a 1:1 adduct. With silver (I) salts, a 2:1 adduct is formed. The silver-bridged complex {[(η 5 -C 5 H 5 ) Os(CH 2 SiMe 3 ) 2 ] 2 (μ-NAgN)}{BF 4 } was isolated in good yield from the reaction between (η 5 -C 5 H 5 )Os(N)(CH 2 SiMe 3 ) 2 and AgBF 4 and was structurally characterized

The new iridium (I) ethylene complexes (η 5 -C 5 H 5 )Ir(η 2 -C 2 H 4 )CO and (η 5 -C 9 H 7 )Ir(η 2 -C 2 H 4 )CO have been prepared. For these complexes, as well as for (η 5 -C 5 H 5 )Ir(η 2 -C 2 H 4 ) 2 and (η 5 -C 9 H 7 )Ir(η 2 -C 2 H 4 ) 2 , the barrier to ethylene rotation about the iridium-ethylene bond axis has been determined by line-shape fitting of variable-temperature 1 H NMR spectra

The osmium methylimido complex [(η5-C5H5)Os(NCH3)(CH2SiMe3)2][SO3CF3], 1, reacts with PPh3 to give both the methyleneamido complex (η5-C5H5)Os(NCH2)(CH2SiMe3)2, 2, and the unique osmium(IV) hydride [(η5-C5H5)Os(H)(PPh3){CHSiMe3PPh2(C6H4)}][SO3CF3], 4. A single-crystal X-ray diffraction study of 4 shows that this molecule has a distorted square pyramidal structure with the center of the cyclopentadienyl ring at the apex. This molecule results from a series of reactions that includes two C−H activation steps: α-hydrogen elimination and orthometalation.

In refluxing chlorobenzene, Ru6C(CO)16PPh3 is converted to Ru6C(CO)13{PPh2(μ-η6-C6H5)} (1), in which one phenyl ring of the PPh3 ligand is coordinated to an adjacent ruthenium atom. Treatment of 1 ...

The anionic organoruthenium complex [PPh4][Ru(N)Me3Br] reacts with NaSSiMe3 to give the trimethylsilanethiolate complex [PPh4][Ru(N)Me3SSiMe3], 1. Reactions of 1 with CsF or with PPh4Cl in nitromethane or acetonitrile produce [PPh4][Ru(N)Me3(SH)], 2. The molecular structure of 2 was determined by X-ray diffraction. Complex 1 reacts with [Os(N)(CH2SiMe3)2(μ-Cl)]2 to form a heterobimetallic complex, [PPh4][Me3(N)Ru(μ-S)Os(N)(CH2SiMe3)2(NCCH3)], 3.

The reactions of triphenylsilane and allyl bromide with [PPN] 2 [Re 7 C(CO) 21 Ir(C 8 H 14 )(CO)] in refluxing THF afforded products in which the substrates were added selectively to the iridium center. The products [PPN] 2 [Re 7 C(CO) 21 Ir(H)(CO)(SiPh 3 )] (1) (77%) and [PPN] [Re 7 C(CO) 21 Ir(η 3 -C 3 H 5 (CO)] (2) (40%) were characterized by analytical and spectroscopic data. The analogous reactions in refluxing cyclohexane with the indenyl complex (η 5 -C 9 H 7 )Ir(C 8 H 14 )(CO) yielded (η 5 -C 9 H 7 ) Ir-(H)(CO)(SiPh 3 ) (3) (78%) and [(η 5 -C 9 H 7 )Ir(η 3 -C 3 H 5 )(CO)]Br (4) (86%), respectively, which were similarly characterized

Selective transformation of H{sub 3}Os{sub 3}(CO){sub 9}({mu}{sub 3}CBr) (1) to a variety of the functionalized triosmium alkylidyne cluster compounds H{sub 3}Os{sub 3}(CO){sub 9}({mu}{sub 3}-CR) (R = CH{sub 2}CH{double bond}CH{sub 2} (2), H (3), CH{sub 3} (4), Ph (5), p-C{sub 6}H{sub 4}CH{sub 3} (6a), CH{sub 2}C(O)Bu{sup t} (7)) is achieved by the treatment of 1 with AgSbF{sub 6} in the presence of silicon and tin nucleophiles. Acyl functional groups (R = C(O)OMe (9), C(O)CH{sub 2}CH{double bond}CH{sub 2} (10), C(O)CH{sub 2}C(O)Bu{sup t} (11)) are also introduced by the reaction of 1 with AgSbF{sub 6} under a CO atmosphere followed by the treatment with nucleophiles.

Synthese des complexes H(O)(CH 2 SiMe 3 ) 4 (H=osmium ou ruthenium) a partir de chlorure de trimethylsilylmethyl de magnesium et de [PPh 4 ] 2 [Os(O) 2 Cl 4 ], [PPN] 2 [Ru(O) 2 Cl 4 ] ou [PPh 4 ] 2 [Os(O) 2 (OSiHe 3 ) 4 . Les complexes sont caracterises par IR, RMN, spectroscopie UV visible et par voltammetrie cyclique. Etude par diffraction RX du complexe Os(O)(CH 2 SiMe 3 ) 4

In refluxing chlorobenzene C60 reacts with Ru5C(CO)15 or with Ru6C(CO)17 to form new complexes, which are isolated following treatment with tertiary phosphines to give the structurally characterized, face-bonded derivatives Ru5C(CO)11(PPh3)(μ3-η2:η2:η2-C60) (1) and Ru6C(CO)12(dppm)(μ3-η2:η2:η2-C60) (2).