PPh(3) and aqueous HClO4 react with an acetone solution of [Pd(C6H4N=NPh-2) (O, O-acac)] (Hacac = acetylacetone; 1:2:7) 1a or [Pd{C6H3(N = NTo)-2,Me-5'}(O,O-acac)] (To = C(6)H(4)Me-4; 1:1:7) 1b to give [Pd(C6H4N = NPh-2)(PPh(3))(acetone)]ClO4 2a or [Pd{C6H3N = NTo)-2,Me-5'}(PPh(3)) (acetone)]ClO4 2b, respectively. They also react with a dichloromethane solution of 1b to afford a mixture of the phosphonium salt [Ph(3)P{C6H3(N(2)To)-2,Me-5}]ClO4 3b and the complex [Pd(O,O-acac)(PPh(3))(2)]ClO4 4. Compounds 2a, 2b or 4 have also been prepared directly by reacting [Pd(R)(mu-Cl)](2) (R = C6H4N = NPh-2 or C6H3(N = NTo)-2,Me-5')], PPh(3) and AgClO4 in acetone or [PdCl2(PPh(3))(2)] with NaClO4 . H2O and Tl(acac), respectively. The phosphonium salts [Ph(3)P{C6H4(N(2)Ph)-2}]ClO4 3a or 3b can be prepared by reacting complexes 2a or 2b, respectively, with PPh(3). The structures of 2a, 3b and 4 have been determined by X-ray diffraction methods. Complex 2a crystallizes in the triclinic space group <P(1)over bar> with Z = 2 in a unit cell of dimensions a = 9.588(6), b = 10.966(5), c = 15.464(8) Angstrom, alpha = 95.82(1), beta = 99.54(1), gamma = 91.21 (1)degrees. Compound 3b crystallizes in the monoclinic space group P2(1)/n with Z = 4 in a unit cell of dimensions a = 10.523(4), b = 28.102(11), c = 10.028(5) Angstrom, beta = 94.41(1)degrees. Compound 4 crystallizes in the monoclinic space group P2(1) with Z = 4 in a unit cell of dimensions a = 9.763(5), b = 33.465(9), c = 12.026(5) Angstrom, beta = 103.06(2)degrees. The structures have been solved from diffractometer data by Patterson and Fourier mehods and refined by full-matrix least squares on the basis of 5539 (2a), 1873 (3b) and 6798 (4) observed reflections to R and R(w) values of 0.0584 and 0.0645 (2a), 0.0617 and 0.0642 (3b), 0.0410 and 0.0478 (4). In 2a the Pd atom is coordinated in a square planar fashion by the P atom from the PPh(3) ligand, by the O(1) atom from the acetone molecule, and by the N and C atoms from the chelating C6H4N = NPh-2 ligand. The structure of the phosphonium salt 3b shows the C-P bond coupling of C6H4(N(2)To)-2,Me-5' with PPh(3). The Pd atom in 4 is in a square planar arrangement involving two P atoms from the PPh(3) ligands and two O atoms from the chelating acac ligand.

The multiple coordination possibilities of 1,8-naphthyridine-2-one (HOnapy) and 5,7-dimethyl-1,8-napthyridine-2-one (HOMe2napy) ligands allow the synthesis of a variety of tri- di- and mononuclear complexes, showing fluxional behaviour and frequent exchange of the coordinated ML2 fragments. Thus, reactions of [M2(μ-OMe)2(cod)2] (cod = 1,5-cyclooctadiene) with HOnapy and HOMe2napy yield the compounds of the general formula [M(μ-OR2napy) (cod)]n (M = Ir, R = Me (1a, 1b, H (2); M = Rh, R = Me (3a, 3b). They crystallise as inconvertible yellow (a) and purple/orange (b) forms and also show a puzzling behaviour in solution. X-ray diffraction studies on both forms (3a, 3b) and spectroscopic data reveal that the yellow forms are mononuclear complexes whilst the dark-coloured crystals contain dinuclear complexes. In solution, the nuclearity of the complexes depends on the solvent. In addition both types of complexes are fluxional. The mixed-ligand complexes [M2(μ-OMe2napy)2(CO)2(cod)] M = Ir (5), Rh (6) have been isolated and characterised; they are found to be intermediates in the synthesis of the trinuclear complexes [M3(μ3-OMe2napy)2(CO)2(cod)2]+ M = Rh (8), Ir (9). Reactions of [IrCl(CO)2(NH2-p-tolyl] with the complexes [Rh(μ-OR2napy)(diolefin)]n followed by addition of a poor donor anion is a general one-pot synthesis for the hetertrinuclear complexes [Rh2Ir(μ3-OR2napy)2(CO)2(diolefin)2]+ (RMe, diolefin = cod (10), tetrafluorobenzo-barrelene (tfbb) (11), 2,5-norbornadiene (nbd) (12); RH, diolefin=cod (13)). This synthesis follows a stepwise mechanism from the mononuclear to the trinuclear complexes in which mixed-ligand heterodinuclear complexes are involved as intermediates of the type [(diolefin)Rh(μ-OMe2napy)2Ir(CO)2]. Heteronuclear complexes which possess the core [RhIr2]3+, such as [RhIr2(μ3-OR2napy)2(CO)2(cod)2]BF4 (RMe (14), H (15)), result from the reaction of 1 or 2 with [Rh(CO)2Sx]+ (S = solvent). The trinuclear complexes undergo two chemically reversible one-electron oxidation processes. The chemical oxidation of 10, 14 and 9 with silver salts gives the mixed-valence trinuclear radicals [Rh2Ir(μ3-OMe2napy)2(CO)2(cod)2]2+ (16), [RhIr2(μ3-OMe2napy)2(CO)2(cod)2]2+ (17) and [Ir3(μ3-OMe2napy)2(CO)2(cod)2]2+ (18), which have been isolated as the perchlorate and tetrafluoroborate salts. The EPR spectrum of 16 indicates that the unpaired electron is essentially in an orbital delocalised on the metals. The molecular structures of the complexes 3a, 3b, 6, 10b and 16a are described. Crystals of 3a are triclinic, P-1, with a = 9.7393(2), b = 14.0148(4), c = 16.0607(4) Å, α = 88.122(3), β = 83.924(3), γ = 87.038(3)°, Z = 4; 3b crystallises in the Pna2i orthorhhombic space group, with a = 16.7541(3), b = 11.7500(8), c = 17.7508(7) Å, Z = 4; complex 6 is packed in the monoclinic space group P2i/c, a = 9.6371(1), b = 11.8054(4), c = 27.2010(9) Å, β = 90.556(4)°, Z = 4; crystals of 10b are monoclinic, P21/n, with a = 17.546(7), b = 13.232(6), c = 17.437(8) Å, β = 106.18(1)°, Z = 4; crystals of 16a are triclinic, P-1, with a = 10.318(4), b = 12.562(6), c = 19.308(8) Å, α = 92.12(8), β = 97.65(9), γ = 90.68(5)°, Z = 2. The five different structures show the coordination versatility of the OMe2napy molecule as ligand, which behaves as a N,N′-chelating (3a), bidentate N,O-donor (3b, 6), or as a tridentate N,N′,O-donor bridging ligand (10b, 16a).

Ph3PSe reacts in toluene with Fe3(CO)12 or Ru3(CO)12 affording a variety of Ph3P-substituted selenido carbonyl clusters. In the case of iron the reaction is unselective, six products (1–6) having been obtained belonging to three different families of clusters. Fe2(μ-Se2)(CO)6−nLn (two products, 3, 5, n = 1, 2), Fe3(μ3-Se)2(CO)9−nLn (three products, 1, 2, 4, n = 0–2) and Fe3(μ3-Se)(μ-CO)(CO)9−nLn (one product, 6, n = 2). In the case of ruthenium, under certain conditions, the reaction is quite selective giving the disubstituted trinuclear cluster Ru3(μ3-Se)2(CO)7(PPh3)2 (8) in very high yield (> 90%). Minor products are the mono- and trisubstituted analogous derivatives 7 and 10 and the tetraruthenium cluster Ru4(μ4-Se)2(μ-CO)2(CO)7(PPh3)2 (9). The crystal structures of the clusters 4, 6, 8 and 9 are described.

The square-planar complex [Ir(C7H4NS2)(CO)(PPh(3))(2)] (1) is obtained in high yield from the reaction of lithium benzothiazole-2-thiolate (LiC7H4NS2) with Vaska's complex, [IrCl(CO)(PPh(3))(2)]. Coordination of the new ligand in 1 and in the homologous rhodium complex should occur through the sulfur atom, as shown by their protonation reactions with HBF4, which give the hydridoiridium(III) complex [IrH(C7H4NS2)(CO)(PPh(3))(2)]BF4 and the rhodium(I) compound [Rh(CO)(PPh(3))(2)(C7H5NS2)]BF4, respectively. The neutral ligand C7H5NS2 reacts with 1 to give [IrH(C7H4NS2)(2)(CO)(PPh(3))(2)] (4). Complex 1 adds dihydrogen, methyl iodide, and dioxygen. The dioxygen complex [Ir(C7H4NS2)(O-2)(CO)(PPh(3))(2)] (7) undergoes an intramolecular oxidation of the carbonyl ligand, catalyzed by water, to yield the carbonate complex [Ir(C7H4NS2)(CO3)(PPh(3))(2)] (8). Labeling studies show that the reaction is multistep and oxygen from water is incorporated into the carbonate ligand. Sulfur dioxide is oxidized by complex 7, but in addition, activation of the carbonyl group occurs by attack of the heterocyclic nitrogen of the benzothiazole-2-thiolate ligand to give [Ir{C(O)NC(S)SC6H4}(SO4)(PPh(3))(2)] (11). In 8 both benzothiazole-2-thiolate and carbonate anions act as N,S- and O,O-chelating ligands. The structure of II shows a C,S-chelating ligand, obtained by an unprecedented incorporation of the carbonyl group of 7 into the benzothiazole-2-thiolate through the heterocyclic nitrogen, in addition to a chelating sulfate ligand.

The benzoylthiourea-functionalized Xerogel XGbztu, obtained from (EtO)3Si(CH2)3NHC(S)NHC(O)Ph by hydrolysis and co-condensation with Si(EtO)4, is able to bind Pd(II) species by reaction with Pd(PhCN)2Cl2. The resulting system XGbztu/Pd is an active catalyst for the hydrogenation of alkynes. After the catalytic runs, supported sulphur-containing metal aggregates have been evidenced by TEM. The non-siloxanized thiourea CH3(CH2)2NHC(S)NHC(O)Ph (Hbztu) has been used as model for the surface binding function of the xerogel. The crystal structures of two Hbztu complexs, namely trans-[Pd(Hbztu)2Cl2], 1, and [Cu(Hbztu)2Cl], 2, have been determined by X-ray diffraction methods.

Reaction of the dioxygen complex [Ir(C7H4NS2)(O2)(CO)(PPh3)2] (C7H4NS2  benzothiazole-2-thiolate) with SO2 produces the unprecedented incorporation of the carbonyl group into the benzothiazole-2-thiolate ligand through the heterocyclic nitrogen, in addition to the oxidation to sulfate, yielding [IrC(O)NC(S)SC6H4(SO4)-(PPh3)2]. bl]

Neutral and cationic rhodium(III) metallated compounds containing a four-membered ring are prepared by different synthetic methods: (i) from rhodium(I) compounds that contain the ligand P(o-ClC6H4)PPh2, by 2c-2e intramolecular oxidative addition; (ii) from metallated dirhodium(II) compounds; (iii) by ligand substitution in [RhCl2{η2-(C6H4)PPh2}{η2-P(o-ClC6H4)Ph2}]. The crystal structures of [RhCl2{η2-(C6H4)PPh2}(η2-dppm)] (2) and of the dichloromethane solvate of [RhCl{η2-(C6H4)PPh2}{η1-P(o-ClC6H4)Ph2}(phen)](SbF6) (11) have been determined by X-ray diffraction methods. In both complexes the Rh atom is in the distorted octahedral arrangement and the metallated phosphine forms, through P and C atoms, a four-membered ring with the metal. A dppm molecule in 2 and a phen molecule in 11 act also as chelating ligands. In 11 the P(o-ClC6H4)PPh2 phosphine behaves as a monodentate ligand.

By reaction of PhNCS with (MeO)3Si(CH2)3NH(CH2)2NH2 (2: 1 molar ratio), a substituted dithiourea has been obtained which affords a new functionalized xerogel (XGditu) by hydrolysis and polycondensation with (EtO)4Si. This material is able to bind metal species, giving systems of potential interest in catalysis. In order to ascertain the nature of the tethered metal species, the non-siloxanized dithiourea PhNHC(S)N(Et)(CH2)2NHC(S)NHPh (2) has been prepared. It reacts with [Ru3(CO)12] to give the complex {(μ-H)RU3(CO) 9}2(SC(NPh)N(Et)(CH2)2NH(PhN)CS} (4), which contains two distinct hydrido carbonyl clusters bound to the two deprotonated thiourea groups.

By reaction of PhNCS with (EtO)3Si(CH2)3NH(CH2)2NH2 (2:1 molar ratio), a substituted dithiourea ligand has been obtained, affording a new functionalized xerogel by hydrolysis and polycondensation with (EtO)4Si. This material is able to bind palladium and copper complexes giving systems of potential interest in catalysis.In order to ascertain the nature of the tethered metal species, the non-siloxanized dithiourea PhNHC(S)N(Et)(CH2)2NHC(S)NHPh has been prepared and reacted with copper(II) chloride. The reaction takes place at room temperature giving a colourless powder and red crystals of the complex [CuCl2{(C7H4NS)-N(CH2)2N(Et)=NPh}], whose structure, fully elucidated by an X-ray study, shows an unexpected N,N-bidentate heterocyclic ligand probably produced by cleavage of a C=S bond followed by a cascade cyclization reaction.

Ru3(CO)12 reacts with a thiourea-functionalized silica xerogel, derived from (EtO)3Si(CH2)3NHC(=S)NHPh, to give a tethered metal carbonyl cluster. This surface organometallic species has the same CO stretching pattern as that of the model compound [(mu-H)Ru3{mu3-SC(NHPr)NPh}(CO)9] (1), obtained from the reaction of Ru3-(CO)12 with N-phenyl-N'-propylthiourea. The molecular structure of 1 has been fully elucidated by an X-ray diffraction study.

The reactions of tetrahedral mixed-metal clusters K[MCo3(CO)12] (M = Fe 1a or Ru 1b) with HgBr2 afforded the pentanuclear clusters [MCo3(CO)12(HgBr)] (M = Fe 2a or Ru 2b) together with hexanuclear clusters [MCo3(CO)12{mu(3)-HgCo(CO)4}] (M = Fe 5a or Ru 5b) in which the mercury atom caps the Co3 face of the precursor. Complexes 5a and 5b were most effectively prepared in dichloromethane by the reaction of 2a or 2b with Na[Co(CO)4]. The reactions with Na[Mo(CO)3(cp)] (cp = eta-C5H5) similarly afforded [MCo3(CO)12{mu(3)-HgMo(CO)3(cp)}] (M = Fe 6a or Ru 6b). The syntheses of the nonanuclear sandwich clusters [mu(6)-Hg{MCo3(CO)12}2] (M = Fe 7a or Ru 7b) are also described. All the complexes have been characterized by IR and UV/VIS spectroscopy. The crystal structure of [FeCo3(mu-CO)3(CO)9{mu(3)-HgMo(CO)3(cp)}] 6a has been determined by X-ray diffraction methods. Crystals are monoclinic, space group P2(1)/c, with a = 28.123(9), b = 8.400(5), c = 25.290(8) angstrom, beta = 114.72(2)-degrees and Z = 8. The structure was solved by direct and Fourier methods and refined by full-matrix least squares to R = 0.0596 for 3016 observed reflections. In the asymmetric unit two crystallographically independent, but essentially identical complexes are present. The complex exhibits a FeCo3 tetrahedron in which the Co3 face is capped by a HgMo(CO)3(cp) fragment such that the FeCo3Hg metal core forms a trigonal bipyramid with the Hg and Fe atoms at the apices. Each Co-Co edge is bridged by an almost symmetrical carbonyl ligand. In addition, three terminal carbonyls are bonded to the Fe atom, and two to each Co atom. The Hg atom has a severely distorted tetrahedral co-ordination involving the three Co atoms and the Mo atom. The structure of 6a is compared with those of 5b and 7b, previously reported.

The title complex has been synthesized by refluxing a toluene solution of Co2(CO)8 and the diyne [(HCCCMe2)2NMe]. It has been characterized by IR and NMR spectroscopy and its structure determined by an X-ray diffraction study. The complex is one of the few examples of a crystallographically characterized cobaltacyclopentadiene derivative. It can be considered to be an intermediate in the cyclization reaction of acetylenic derivatives catalyzed by cobalt carbonyls, and a model for the intermediates in heterocycle formation from diynes and nitriles catalyzed by Co0 complexes.

The new unsaturated hydride [Mn2(mu-H)2(CO)6(mu-dppm)] (1) is prepared by treatment of [Mn2(mu-Cl)2(CO)6(mu-dppm)] with 4 equiv of Li[HBEt3] in tetrahydrofuran at room temperature. 1 reacts with 1-alkynes (R = H, Ph, (t)Bu, COOMe) at room temperature to give either hydrido-alkenyl complexes [Mn2(mu-H)(mu(2),eta(1),eta(2)-CR = CH2)(CO)6(mu-dppm)] (R = H (3a), Ph (3b)) or alkenylidene species [Mn2(mu(2),eta(1),eta(2)-C = CHtBu)(CO)6(mu-dppm)] (4c) and [(CO)3Mn(mu-dppm){mu-C = CHC(Activated O)OMe}MN(CO)3] (6). The photochemical reaction of [Mn2(CO)8(mu-dppm)] (2) with 1-alkynes (R = H, Ph, (t)Bu, CH3OCH2) at -20-degrees-C results in the formation of vinylidene [Mn2(mu(2),eta(1),eta(2)-C = CHR)(CO)6(mu-dppm)] (R = Ph (4b), (t)Bu (4c), CH3OCH2 (4d)), hydrido-alkynyl [Mn2(mu-H)(mu(2),eta(1),eta(2)-C2R)(CO)6(mu-dppm)] (R = H (5a), Ph (5b), (t)Bu (5c), CH3OCH2 (5d), or 5-oxo-2-furanylidene complexes [(CO)4Mn(mu-dppm){mu(2),eta(1),eta(4)-C-CH = C(R)C(O)O}Mn(CO)2] (R = H (7a), CH3OCH2 (7d)) and [Mn2(mu-CO){mu(2),eta(1),eta(1)- Activated C-CH = C(R)C(O)O}(CO)6(mu-dppm)] (R = H (8a), CH3OCH2 (8d)). The relative amounts of the above species depend strongly on the nature of the alkyne and the reaction solvent. The 5-oxo-2-furanylidene ligands in 7 bind the dimetal moiety in a novel mu(2),eta(1),eta(4)-fashion acting as a 6-electron donor. The alkenylidene complexes 4b and 4c can also be obtained through UV irradiation of the alkenyl complex 3a in the presence of an excess of 1-alkyne (R = Ph, (t)Bu). Unexpectedly, these complexes isomerize spontaneously in solution at room temperature to yield the corresponding hydrido-alkynyls 5b and 5c. The latter regenerate their vinylidene precursors 4b and 4c by treatment with Li[AlH4] followed by addition of HBF4 to the resulting mixture. Complexes 3a, 5a-d, and 7 are stereochemically nonrigid in solution. In the case of the alkynyl species 5 the fluxional process appears to be especially fast, as even evidence for incipient coalescence is not observed down to -90-degrees-C. The structures of 4c, 5b, 6, 7d, and 8d have been fully elucidated by X-ray diffraction studies.

With the aim of inducing a mu-SiF interaction between two metal centres, MeO was replaced by F on the silicon atom involved in mu-SiO bonding with a bimetallic unit by the reaction of mer-[(OC)3 activated Fe{mu-Si(OMe)2(OMe)}(mu-dppm)PdCl)] 1 (dppm = Ph2PCH2PPh2) with BF3. However, the desired complex mer-[(OC)3 activated Fe{mu-SiF2(F)}(mu-dppm)PdCl] 3 could only be characterised in solution. From the solution structure of the reaction intermediate mer-[(OC)3 activated Fe{mu-SiF2(OMe)}(mu-dppm)PdCl] 2 where a MeO --> Pd interaction in preference to F --> Pd is suggested on the basis of spectroscopic data, it appears that the dative F --> Pd interaction is weaker than the corresponding MeO --> Pd one. In the presence of an excess of BF3, rupture of the Fe-Si bond of 3 eventually occurred in CH2Cl2, resulting in the formation of [(OC)3 activated Fe(mu-Cl)(mu-dppm)PdCl] 4a. When the complex mer-[{(MeO)3Si}(OC)3 activated Fe(mu-dppm)PtH(PPh3)] 5 was treated with BF3.Et2O, the trifluorosilyl derivative mer-[(F3Si)(OC)3 activated Fe(mu-dppm)PtH(PPh3)] 6 was obtained and isolated in 87% yield. The structure of its benzene solvate 6.0.5C6H6 was determined by X-ray diffraction: triclinic, space group P1BAR, a = 17.692(7), b = 13.084(5), c = 11.031(5) angstrom, alpha = 112.16(1), beta = 91.31(2), gamma = 101.71(1)-degrees and Z = 2. It has been solved by Patterson and Fourier methods and refined by full-matrix least squares to R = 0.0408 for 5870 observed reflections. The Fe and Pt atoms are at a distance of 2.661(1) angstrom, consistent with a metal-metal bond. The nearly square-planar co-ordination of Pt involves also one P atom from dppm, one PPh3 and a hydride. The co-ordination of Fe is completed by three carbonyl groups, a P atom of the dppm ligand, and the SiF3 ligand. Noteworthy are the weak intramolecular interactions between the hydride and two F atoms from the SiF3 ligand [H...F2.39(7) and 2.50(6) angstrom]. The IR and NMR (H-1, P-31-{H-1} and F-19-{H-1}) spectra of the new complexes are reported and discussed.

C 6 H 6 NO 2 + •[PtCl 3 (C 2 H 6 OS)] − cristallise dans Pbca avec a=9,994, b=21,268, c=13,200 A, Z=8; affinement jusqu'a R=0,031. La structure est composee d'anions complexes [PtCl 3 (Me 2 SO)] − et de cations protones de 2-carboxypyridinium, lies par une liaison hydrogene impliquant l'atome N protone du pyridinium et un atome Cl du complexe de platine

Complexes [PPh3(CH2Ph)][Pd(R)Cl2(CO)] [R = C6H3Me-2,NO2-6 (1), C6H2(NO2)3-2,4,6 (2)] can be isolated by carbonylation, at room temperature and atmospheric pressure, of [PPh3(CH2Ph)]2[Pd(R)Cl(mu-Cl)]2. Complex 1 is the first example of an organocarbonylpalladium(II) complex characterized by an X-ray diffraction study. Crystals are triclinic, space group P1, with Z = 2 in a unit cell of dimensions a = 10.446 (5) angstrom, b = 12.538 (7) angstrom, c = 14.148 (6) angstrom, alpha = 65.40 (2)-degrees, beta = 74.17 (2)-degrees, and gamma = 72.83 (2)-degrees. The structure has been solved by Patterson and Fourier methods and refined by full-matrix least squares on the basis of 1274 observed reflections to R and R(w) values of 0.0319 and 0.0440. In the anionic complex the Pd atom is in a square-planar arrangement with two Cl atoms in cis positions and the carbonyl group and the 2-methyl-6-nitrophenyl ligand trans to them. The Pd-CO bond [Pd-C = 1.853 (10) angstrom] is discussed on the basis of the IR and X-ray data.

A comparison between the structures of closo trigonal-bipyramidal acetylene and acetylide clusters with M3C2 frameworks is made. The synthesis of (eta-5-C5H5)NiFe2(CO)6(mu-3-eta-2-C = CPr(i)) (1) from [(eta-5-C5H5)Ni(CO)]2, Ph2PC = CPr(i), and Fe2(CO)9 is described. X-ray structural analyses of (eta-5-C5H5)NiFe2(CO)5(L)(mu-3-eta-2-C = CR) (L = CO, R = Pr(i), 1; L = PPh3, R = Bu(t), 2) are described. Crystal data: 1, C16H12Fe2NiO6, M(r) = 470.67, triclinic space group P1BAR, a = 14.769 (7) angstrom, b = 14.824 (6), c = 8.708 (4), alpha = 91.77 (2)degrees, beta = 96.45 (2)degrees, gamma = 109.27 (2)degrees, V = 1784 (1) angstrom 3, Z = 4; 2, C35H29Fe2NiO5P.0.5C7H16, M(r) = 781.10, space group P2(1)/c, a = 10.058 (3) angstrom, b = 13.225 (6) angstrom, c = 26.906 (8) angstrom, beta = 96.08 (2)degrees, V = 3559 (2) angstrom 3, Z = 4. The structures of 1 and 2 were solved and refined on the basis of 5143 and 3289 observed intensities measured on Siemens AED and Syntex P2(1) diffractometers. Final R and R(w) values were 0.048 and 0.054 for 1 and 0.056 and 0.066 for 2. There are significant structural differences between the closo trigonal-bipyramidal M3C2 skeletons of the acetylide and acetylene clusters. In particular the M-C-alpha distances are much shorter in the acetylides, perhaps indicating substantial pi-character to the metal-sigma-acetylide bond. The intrapolyhedral M-C-alpha-C-beta angles are much larger in the acetylides than in the acetylenes. The C-alpha-R fragments in the mu-3-eta-2- perpendicular-to -acetylene clusters approximate more closely to an equatorial component of a trigonal bipyramid than the ''bare'' C-alpha in the mu-3-eta-2-acetylides. The acetylides show a closer structural resemblance to the M4 cluster carbides.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTReactions of HC.tplbond.CCMe2NHCOR alkynes with M3(CO)12 carbonyl (M = Ru, R = C6H9, Ph; M = Os, R = C6H9). Synthesis and crystal structure of Ru4(CO)11(HC.tplbond.CCMe2NHCOC6H9), a butterfly cluster showing an interaction between a wingtip metal and the amide COGiovanni Predieri, Antonio Tiripicchio, Marisa Tiripicchio Camellini, Mirco Costa, and Enrico SappaCite this: Organometallics 1990, 9, 6, 1729–1734Publication Date (Print):June 1, 1990Publication History Published online1 May 2002Published inissue 1 June 1990https://pubs.acs.org/doi/10.1021/om00156a009https://doi.org/10.1021/om00156a009research-articleACS PublicationsRequest reuse permissionsArticle Views55Altmetric-Citations22LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-AlertscloseSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

The reaction of PPh2(CHCH2) with [Os3(CO)12] in aliphatic hydrocarbons gives the monosubstituted derivative [Os3(CO)11(Ph2PCHCH2)] in medium yield. By contrast [Ru3(CO)12] gives, as the final product, [Ru3(µ-H)(CO)8(Ph2PCHCH2)(µ3-Ph2PCHCH)](2) in high yield; this reaction represents an example of oxidative addition of PPh2(CHCH2), occurring in two steps and presumably favoured by the t.l.c. support material used during purification. These compounds have been characterized by elemental analyses and spectroscopy, in particular 1H, 13C, and 31P n.m.r. The structure of complex (2) has also been determined by X-ray diffraction methods. It crystallizes in the orthorhombic space group P212121, with Z= 4 in a unit cell of dimensions a= 15.984(6), b= 22.441(7), and c= 10.327(4)Å. The structure has been solved from diffractometer data by direct and Fourier methods and refined by full-matrix least squares to R= 0.0430 for 1 634 observed reflections. The structure consists of a scalene triangle of Ru atoms [Ru(1)–Ru(2) 2.759(3), Ru(1)–Ru(3) 3.024(3) and Ru(2)–Ru(3) 2.862(3)Å] bound to eight terminal carbonyls. The PPh2(CHCH2) is σ-bound to one Ru atom through the P atom, while the Ph2PCHCH ligand interacts with all three metals, being σ-bound to two Ru atoms (through the P and C atom) and π-bound to the third Ru atom through the double bond. This latter ligand is formed by stepwise oxidative addition of PPh2(CHCH2) to the cluster, with hydrogen transfer to give a hydride ligand bridging the longest edge of the cluster.