Novel Alkyne And Phosphaalkyne Coupling On An Ir4 Cluster: Synthesis And Molecular Structure Of [ir4(μ-co)(co) 7{μ4-η3-ph2 Pc(h)c(ph)pcbut}(μ-pph2)]

The cluster compound [(μ-H)Ir4(CO)9(Ph 2PCCPh)(μ-PPh2)] 1 reacts with the phosphaalkyne ButCP to yield [Ir4(μ-CO)(CO) 7{μ4-η3-Ph2 PC(H)C(Ph)PCBut}(μ-PPh2)] 3, containing the novel 2-phosphabutadienylphosphine fragment as a result of the coupling of Bu tCP with the diphenylphosphinoalkyne ligand and incorporation of the cluster bound H atom.161869187

Magnetic susceptibilities, specific heat, and crystal structure of four S = 3/2, three-dimensional antiferromagnets

The zero-field, ac magnetic susceptibilities of single crystals of four S=3/2 trigonal salts containing the tris(1,2-diaminoethane)chromium(III) cation, [Cr(en)3]3+, and heat-capacity measurements on one of them, [Na(OH2)6][Cr(en)3]2Cl7, are reported. The crystal structures of two of them, [Na(OH2)6][Cr(en3]2Cl7 and [Na(OH)2)6][Cr(en)3]2Br6Cl, have been determined. They both belong to the trigonal P3¯cl space group, with a=11.513(2), c=15.566(6) Å; Z=2; and a=11.740(5), c=16.008(9) Å; Z=2, respectively, and contain discrete octahedral hexaquasodium (i) cations. The salt [K(OH2)6][Cr(en)3]2Cl7 appears to be isomorphous with its sodium analog, and [Cr(en)3]Cl3·3H2O belongs to the same space group. The magnetic measurements on the four salts extend over the temperature interval 60 mK to 4.2 K, and antiferromagnetic ordering is found in all of them. The zero-field-splitting energy is of the same order of magnitude as the magnetic exchange energy. The susceptibility data have been fitted with the parameters 2D/kB=-0.091(8) K, g?=1.994, g¿=1.988, and zJ/kB=-0.061(2) K for [Cr(en)3]Cl3·3H2O; 2D/kB=-0.058(8) K, g?=2.01, g¿=2.00, and zJ/kB=-0.068(4) K for [Na(OH2)6][Cr(en)3]2Cl7; 2D/kB =-0.060(8) K, g?=1.993, g¿=1.951, and zJ/kB=-0.046(4) K for [K(OH2)6][Cr(en)3]2Cl7; and 2D/kB=+0.064(8) K, g?=2.001, g¿=1.991, and zJ/kB=-0.066(4) K for [Na(OH2)6][Cr(en)3]2Br6Cl, where longitudinal (¿) and transverse (¿) refer to the unique threefold crystallographic axis. The ordering temperatures are 0.124(5), 0.116(5), 0.093(5), and 0.112(5) K, respectively. The easy axis for the chloride compounds lies parallel to the longitudinal axis, whereas the easy axis for the bromide lies in the transverse plane. Heat-capacity measurements on [Na(OH2)6][Cr(en)3]2Cl7 confirm that magnetic ordering takes place at 0.112(5) K. The heat-capacity curve and magnetic entropy calculations agree with the three-dimensional character of the ordering of an S=3/2, effective bcc magnetic lattice

Catalytic hydroacetylenation of carbodiimides with homoleptic alkaline earth hexamethyldisilazides

The homoleptic alkaline earth hexamethyldisilazides, [M{N(SiMe3)2}2(THF)2] (M = Mg, Ca, Sr), are shown to be efficient precatalysts for the hydroacetylenation of organic carbodiimides with alkyl- and arylacetylenes.</p

Synthesis and characterisation of a series of 1,2-phenylenedioxoborylcyclopentadienyl-metal complexes [Ti(IV), Zr(IV), Hf(IV), La(III), Ce(III), Yb(III), Sn(II) and Fe(II)]

The preparation of a series of 1,2-phenylenedioxoborylcyclopentadienyl\u2013metal complexes is described. These are of formula [M{g5-C5H4(BX)}Cl3] [M = Ti and X = CAT (2a), CATt (2b) or CATtt (2c); X = CATtt and M = Zr (4a) or Hf (4b)], [M{g5- C5H4(BX)}2Cl2] [M = Zr, X = CAT (3a) or CATt (3c); orM = Hf, X = CAT (3b) or CATt (3d)], [M{(l-g5-C5H3BCAT)2 SiMe2}Cl2] [M = Zr (5a) or Hf (5b)], [M{g5-C5H3(BCAT)2}Cl3] [M = Zr (6a) or Hf (6b)], [M{g5-C5H4BCAT}3(THF)] [M = La (7a), Ce (7b) or Yb (7c)], [Sn{g5-C5 H4(BCATt)}Cl](8) and [Fe{g5-C5H4(BCATt)}2] (9). The abbreviations refer to BO2C6H4-1,2 (BCAT) and the 4- But (BCATt) and the 3; 5-But 2 (BCATtt) analogues. The compounds 2a\u20139 have been characterised by microanalysis, multinuclear NMR and mass spectra. The single crystal X-ray structure of the lanthanum compound 7a is presented

Novel C-h Activation In A Bis-tetrairidium Carbonyl Complex Of The Sandwich Compound [fe(η5-c5h5)(η5-p 3c2but 2)]: Crystal And Molecular Structures Of [ir4(co)11{fe(η5-c5h 5)(η5-p3c2bu(t) 2)}]

The syntheses and structural determinations of novel complexes of the type [Ir4(CO)11L] {L = [Fe(η5-P3C2But 2)(η5s-P2C3But 3)] or [Fe(η5-C5H5)(η5-P 3C2But 2)]} and [HIr4(CO)10-(μ-Fe(η5-C5H 5)(η5-P3CH2(CMe 2)CBut)}Ir4(CO)11], involving an unusual C-H activation, are described.3441443Bartsch, R., Hitchcock, P.B., Nixon, J.F., (1987) J. Chem. Soc., Chem. Commun., p. 1146Binger, P., Glaser, G., (1994) J. Organomet. Chem., 479, pp. C28Bartsch, R., Hitchcock, P.B., Nixon, J.F., (1988) J. Organomet. Chem., 340, pp. C37Müller, C., Bartsch, R., Fischer, A., Jones, P.G., (1993) J. Organomet. Chem., 453, pp. C16Nixon, J.F., (1988) Chem. Rev., 88, p. 1327Nixon, J.F., (1991) Endeavour, 15, p. 49(1993) Chem. Ind., p. 404Bartsch, R., Gelessus, A., Hitchcock, P.B., Nixon, J.F., (1992) J. Organomet. Chem., 430, pp. C10Müller, C., Bartsch, R., Fischer, A., Jones, P.G., (1993) Polyhedron, 12, p. 1383Chini, P., Ciani, G., Garlaschelli, L., Manassero, M., Martinengo, S., Sironi, A., Canziani, F., (1978) J. Organomet. Chem., 152, pp. C35Besançon, K., Laurenczy, G., Lumini, T., Roulet, R., Gervasio, G., (1993) Helv. Chim. Acta, 76, p. 2926. , and references thereinMann, B.E., Vargas, M.D., Katthar, R., (1992) J. Chem. Soc., Dalton Trans., p. 1725Mann, B.E., Pickup, B.T., Smith, A.K., (1989) J. Chem. Soc., Dalton Trans., p. 889Churchill, M.R., Hutchinson, J.P., (1978) Inorg. Chem., 17, p. 3528Della Pergola, R., Garlaschelli, L., Martinengo, S., Demartin, F., Manassero, M., Sansoni, M., (1987) Gazz. Chim. Ital., 117, p. 245Shapley, J.R., Stuntz, G.F., Churchill, M.R., Hutchinson, J.P., (1979) J.Chem. Soc., Chem. Commun., p. 219Vargas, M.D., Pereira, R.M.S., Braga, D., Grepioni, F., (1993) J. Chem. Soc., Chem. Commun., p. 1008Nicholls, J.N., Raithby, P.R., Vargas, M.D., (1986) J. Chem. Soc., Chem. Commun., p. 1617Demartin, F., Manassero, M., Sansoni, M., Garlaschelli, L., Raimondi, C., Martinengo, S., Canziani, F., (1981) J. Chem. Soc., Chem. Commun., p. 52

1,2,3-triphenyiphosphirene Derivatives Of The Iridium Carbonyl Clusters [hir4(co)9l(μ-pph2)] (l = Co, Pph3) Resulting From Substitution, Insertion And Hydrometallation Processes 1

1,2,3-Triphenylphosphirene reacts with [HIr4(CO)10(μ-PPh2)] 1, at room temperature, to afford [Ir4(CO)8(μ3-μ 2PhPCPh=CPh)(μ-PhPCPh=CHPh)(μ-PPh2)] 2 which contains the phosphametallacycle (μ3-η2-PhPCPh=CPh) and the phosphidoalkenyl (μ-PhPCPh=CHPh) ligands arising from insertion and hydrometallation processes respectively. In contrast, the PPh3 derivative of 1, [HIr4(CO)9(PPh3)(μ-PPh2)] 3, reacts selectively at room temperature with the phosphirene to give only CO substitution products, [HIr4(CO)9-n(PPh3)(η 1-PhPCPh=CPh)n(μ-PPh2)] (n=1,4 and 2, 5) which are the first carbonyl cluster compounds containing intact η1-ligated phosphirene rings. High yield conversion of compound 4 into the phosphametallacycle species [HIr4(CO)7(PPh3)(μ3-η 2-PhPCPh=CPh)(μ-PPh2)] 6 is achieved under mild thermolytic conditions. An insight into the mechanism of formation of 2 was given by the reaction of the phosphirene ring with the anion [Ir4(CO)10(μ-PPh2)]- 1a derived from 1, followed by protonation, which gave [HIr4(CO)8(μ3-η 2-PhPCPh=CPh)(μ-PPh2)] 7, which is analogous to 6 with a CO ligand replacing PPh3. Quantitative conversion of the hydride phosphametallacycle 7 into the labile phosphidoalkenyl cluster [Ir4(CO)n(μ-PhPCPh=CHPh)(μ-PPh2)] 8 is easily achieved in the presence of CO (1 atm, RT, 2 h), as a result of the reductive elimination of a C-H group. Compound 8 undergoes facile CO dissociation and co-ordination of the phosphidoalkenyl C=C bond to the metal centre to produce [Ir4(CO)9(μ3-η 3-PhPCPh=CHPh)(μ-PPh2)] 9. The molecular structures of compounds 2,4,6 and 9 were established by X-ray diffraction studies and the structures of all compounds in solution were investigated by a combination of 1H and 31P{1H} NMR studies. © The Royal Society of Chemistry 2000.1525272536Mathey, F., (1990) Chem. Rev., 90, p. 997Mathey, F., Regitz In, M., (1996) Comprehensive Heterocyclic Chemistry II, , Pergamon, OxfordDillon, K.B., Mathey, F., Nixon, J.F., (1998) Phosphorus: the Carbon Copy, , John Wiley, ChichesterMercier, F., Deschamps, B., Mathey, F., (1989) J. Am. Chem. Soc, 111, p. 9098Marinetti, A., Mathey, F., Fischer, J., Mitschier, A., (1982) J. Am. Chem. Soc., 104, p. 4484Marinetti, A., Mathey, F., (1985) J. Am. Chem. Soc., 107, p. 4700Al-Juaid, S.S., Carmichael, D., Hitchcock, P.B., Lochschmidt, S., Marinetti, A., Mathey, F., Nixon, J.F., (1988) J. Client. Soc., Chem. Commun., p. 1156Marinetti, A., Mathey, F., (1987) Tetrahedron Lett., 28, p. 5021Espinosa Ferao, A., Deschamps, B., Mathey, F., (1993) Bull. Soc. Chim. Fr., 130, p. 695Marinetti, A., Fischer, J., Mathey, F., (1985) J. Am. Chem. Soc., 107, p. 5001Carmichael, D., Hitchcock, P.B., Nixon, J.F., Mathey, F., Pidcock, A., (1986) J. Chem. Soc., Chem. Commun., p. 762Al-Juaid, S.S., Carmichael, D., Hitchcock, P.B., Marinetti, A., Mathey, F., Nixon, J.F., (1991) J. Client. Soc., Dalton Trans., p. 905Ajulu, F.A., Carmichael, D., Hitchcock, P.B., Mathey, F., Meidine, M.F., Nixon, J.F., Ricard, L., Riley, M.L., (1992) J. Chem. Soc., Client. Commun., p. 750Carmichael, D., Hitchcock, P.B., Mathey, F., Nixon, J.F., Ricard, L., (1993) J. Client. Soc., Dalton Trans., p. 1811Arce, A.J., De Sanctis, Y., Machado, R., Campparelli, M.V., Mansur, J., Deeming, A.J., (1995) Organometallics, 14, p. 3592Livotto, F.S., Raithby, P.R., Vargas, M.D., (1993) J. Chem. Soc., Dalton Trans., p. 1797Araujo, M.H., (1995), Ph.D. Thesis, Universidade Estadual de Campinas, BrazilVargas, M.D., Pereira, R.M.S., Braga, D., Grepioni, F., (1993) J. Chem. Soc., Chem. Commun., p. 1008(1999) J. Bra:. Chem. Soc., 10, p. 35Benvenutti, M.H.A., Vargas, M.D., Braga, D., Grepioni, F., Parisini, E., Mann, B.E., (1993) Organomelallics, 12, p. 2955Benvenutti, M.H.A., Vargas, M.D., Braga, D., Grepioni, F., Mann, B.E., Naylor, S., (1993) Organomelallics, 12, p. 2947Benvenutti, M.H.A., Hitchcock, P.B., Nixon, J.F., Vargas, M.D., (1994) J. Chem. Soc., Chem. Commun., p. 1869Araujo, M.H., Hitchcock, P.B., Nixon, J.F., Vargas, M.D., (1998) J. Bra:. Chem. Soc., 9, p. 563Carty, A.J., Mac Laughlin, S.A., Nucciaroni, D., (1987) Phosphorus 31-NMR Spectroscopy in Stereochemical Analysis of Organic Compounds and Metal Complexes, , ed. J. G. Verkade and L. D. Quin, VCH, Weinheim, ch. 16Browning, J., Dixon, K.R., Meanwell, N.J., (1993) Inorg. Ciim. Acta, 213, p. 171Berry, D.E., Browning, J., Dehghan, K., Dixon, K.R., Meanwell, N.J., Phillips, A., (1991) Inorg. Client., 30, p. 396Ros, R., Scrivanti, A., Albano, V.G., Braga, D., Garlaschelli, L., (1986) J. Chem. 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Synthesis And Structural Characterization Of [ir4(μ-co)(co)7{μ4-η3-ph 2pc(h)c(ph)pcbut}(μ-pph2)]: Alkyne-phosphaalkyne Coupling And Formation Of A Novel 2-phosphabutadienylphosphine Ligand

Reaction of [Ir4(μ-H)(CO)9(Ph2PC=CPh)(μ-PPh 2)]1 with PsCBut in CH2Cl2, at 35°C, for 4 h yields the novel compound [Ir4(μ-CO)(CO)7{μ4-η3-Ph 2PC(H)C(Ph)PCBut}(μ-PPh2)] 2, which contains the 2-phosphabutadienylphosphine chain. Compound 2 is also formed upon thermolysis of [Ir4(CO)10(Ph2PC=CPh)(PPh2H)] 3 in the presence of P=CBut in thf, at 40°C, for 48 h. Small amounts of [Ir4(μ-CO)(CO)7(μ3-η 2-HCCPh)(μ-PPh2)2] 4 are always obtained from both reactions, because of the competing rates of the transformations of 1 and 3 into 4 and of their reactions with P≡CBut. Compound 2 was characterized by analytical and spectroscopic studies such as FAB ms, 1H, 31P, 13C, 2D 31P-1H HETCOR, nOe difference and DEPT NMR experiments, which led to its formulation and established the coupling between the coordinated Ph2PC≡CPh and P≡CBut and the migration of the hydride to the Cα of the Ph2PC≡CPh ligand. However, it was impossible to establish unambiguously if cleavage of the P-Cspbond of the Ph2PC≡CPh ligand had occurred and the mode of interaction of the organophosphorus chain. An X-ray diffraction study of compound 2 established a butterfly arrangement of iridium atoms with the new ligand interacting with the metal framework via four σ bonds and the PPh2 phosphorus lone pair.96563570Sappa, E., Tiripicchio, A., Braunstein, P., (1983) Chem. Rev., 83, p. 203Shapley, J.R., McAteer, C.H., Churchill, M.R., Biondi, L.V., (1984) Organometallics, 3, p. 1595Riaz, V., Curtis, M.D., Rheingold, A., Haggerty, B.S., (1990) Organometallics, 9, p. 2647Matsuzaka, H., Mizobe, Y., Nishio, M., Hidai, M., (1991) J. Chem. Soc., Chem. Commun., p. 1011Pereira, R.M.S., (1996), Ph.D. Thesis, Universidade Estadual de Campinas, BrazilNixon, J.F., (1988) Chem. Rev., 88, p. 1327(1993) Chem. Ind., p. 404(1995) Coord. Chem. Rev., 145, p. 201(1995) Chem. Soc. Rev., p. 319Dillon, K.B., Mathey, F., Nixon, J.F., (1998) Phosphorus: The Carbon Copy, , Ed. John WileyImhof, W., Huttner, G., (1993) J. Organomet. Chem., 447, p. 31Binger, P., Milczarek, R., Mynott, R., Regitz, M., (1987) J. Organomet. Chem., 323, pp. C35Regitz, M., (1990) Multiple Bond and Low Coordination in Phosphorus Chemistry, , Ed. Regitz, M.Scherer, O.J., Georg Thieme Verlag, Stuttgart, Chapter 2Appel, R., (1990) Multiple Bonds and Low Coordination in Phosphorus Chemistry, , Ed. Regitz, M.Scherer, O.J., Georg Thieme Verlag, Stuttgart, Chapter 2Benvenutti, M.H.A., Vargas, M.D., Braga, D., Grepioni, F., Mann, B.E., Naylor, S., (1993) Organometallics, 12, p. 2947. , and references thereinSappa, E., Pasquinelli, G., Tiripicchio, A., Tiripicchio-Camellini, M., (1989) J. Chem. Soc., Soc., Dalton Trans., p. 601. , and references thereinChi, Y., Hwang, D.-K., Chen, S.-F., Liu, L.-K., (1989) J. Chem. Soc., Chem. Commun., p. 1540Chi, Y., Huttner, G., Imhof, W., (1990) J. Organomet. Chem., 354, p. 93Benvenutti, M.H.A., Hitchcock, P.B., Nixon, J.F., Vargas, M.D., (1994) J. Chem. Soc., Chem. Commun., p. 1869Araujo, M.H., (1995), Ph.D. Thesis, Universidade Estadual de Campinas, BrazilVerkade, J.G., Mosbo, J.A., (1987) Phosphorus-31 NMR Spectroscopy in Stereo Chemical Analysis, , Ed. Verkade, J.G. and Quin, L.D., VHC, Chapter 13Doherty, S., Corrigan, J.F., Carty, A.J., Sappa, E., Adv. Organomet. Chem., 37, p. 39Mann, B.E., Pickup, B.T., Smith, A.K., (1989) J. Chem. Soc., Dalton Trans., p. 889Mingos, D.M.P., May, A.S., (1990) Structural and Bonding Aspects of Metal Cluster Chemistry, 16, p. 4833. , Shriver, D.F.Kaesz, H.D.Adams, R.D., eds., VHCPereira, R.M.S., Fijiwara, F.Y., Vargas, M.D., Braga, D., Grepioni, F., (1997) Organometallics, 16, p. 4833Vargas, M.D., Pereira, R.M.S., Braga, D., Grepioni, F., (1993) J. Chem. Soc., Chem. Commun., p. 1008Benvenutti, M.H.A., Vargas, M.D., Braga, D., Grepioni, F., Parisini, E., Mann, B.E., (1993) Organometallics, 12, p. 2955. , and references thereinHobbold, M., Streubel, R., Benvenutti, M.H.A., Hitchcock, P.B., Nixon, J.F., (1997) Organometallics, 16, p. 3726Bedford, R.B., Hill, A.F., Jones, Q., White, A.J.P., Wilton-Ely, J.D.E.T., (1997) J. Chem. Soc., Dalton Trans., p. 139Binger, P., Sandmeyer, F., Krüger, C., Jörg, K., Goddard, R., Erker, G., (1994) Angew. Chem. Int. Ed. Engl., 33, p. 197Sappa, E., Pasquinelli, G., Tiripichio, A., Camellini, M.T., (1989) J. Chem. Soc., Dalton Trans., p. 601. , and references thereinMann, B.E., (1988) Adv. Organomet. Chem., 28, p. 397. , and references therein(1989) CAD-4 Software. Version 5.0, , Enraf-Nonius, The NetherlandsSheldrick, G.M., (1985) SHELXS-86. Program for the Solution of Crystal Structures, , University of Gottingen GermanySheldrick, G.M., (1993) SHELXL-93. Program for Crystal Structure Refinement, , University of Gottingen, GermanyWatkin, D.J., Pearce, L.J., (1993) CAMERON. An Interactive Graphics Editor, , University of Oxford, Englan

First Evidence For Two Different μ-η1-η1- And μ-η1-η2- Co-ordination Modes Of The P3c2but 2 Ring Of [fe(η5-p3c2but 2)(η5-c5h5)] To A Same Cluster Fragment.

Investigation of the solution structures of [Ir4(CO)11L] (L = [Fe(η5-P3C2But 2)(η5-C5H5)] (1) and [Fe(η5-P3C2But 2)(η5-P2C3But 3)] (2) by 13C and 31P NMR spectroscopy showed that, at 163K, 1 exists in the form of two isomers with bridged and non-bridged structures, in a 1:0.15 ratio, respectively, whereas 2 exists only in the bridged form. At RT, 1,2 shift of η5-P3C2But 2 ring was only observed for compound 2. Where as 2 loses CO readily in solution to give [Ir4(CO)10{μ-η1-η 1-[Fe(η5-P3C2But 2)(η5-P2C3But 3)}] (3), activation with Me3NO was necessary to produce [Ir4(CO)10{[Fe(η5-P3C 2But 2)(η5-C5H 5)}] (4), obtained in the form of two non-interconverting isomers 4a and 4b, which were not able to be separated. A single crystal X-ray diffraction study of isomer4a established that the [Fe(η5-P3C2But 2)(η5-C5H5)] ligand bridges one of the edges of the Ir4 tetrahedron, interacting via the lone electron pair of one of the adjacent P atoms and in an η2- mode via the P-P double bond of the η5-P3C2But 2 ring and that all CO ligands arc terminally bonded. Variable temperature31P{1H} NMR spectroscopy evidenced a fluxional process involving interactions between the Ir1 and Ir2 atoms and the lone pair on P1, the P1-P2 bond, and the lone pair on P2. According to multinuclcar NMR, cluster 4b has similar structure to compound 3, with the η5-P3C2But 2 ring co-ordinated in aη1-η1- mode via the two adjacent P atoms, and all CO ligands bonded terminally.114405411Dillon, K.B., Mathey, F., Nixon, J.F., (1998) Phosphorus the Carbon Copy, , John Wiley and Sons, Chichester, and references cited thereinBartsch, R., Hitchcock, P.B., Nixon, J.F., (1988) J. Organomet. Chem., 340, pp. C37Müller, C., Bartsch, R., Fischer, A., Jones, P.G., Schmutzler, R., (1996) J. Organomet. Chem., 512, p. 141Müller, C., Bartsch, R., Fischer, A., Jones, P.G., (1993) Polyhedron, 12, p. 1383Bartsch, R., Gelessus, A., Hitchcock, P.B., Nixon, J.F., (1992) J. Organomet. Chem., 430, pp. C10Callaghan, C.S.J., Hitchcock, P.B., Nixon, J.F., (1999) J. Organomet. Chem., 584, p. 87Müller, C., Bartsch, R., Fischer, A., Jones, P.G., (1993) J. Organomet. Chem., 453, pp. C16Bartsch, R., Gelessus, A., Hitchcock, P.B., Nixon, J.F., (1992) J. Organomet. Chem., 430, pp. C10Benvenutti, M.H.A., Hitchcock, P.B., Nixon, J.F., Vargas, M.D., (1996) Chem. Commun., 441Benvenutti, M.H.A., Hitchcock, P.B., Nixon, J.F., Vargas, M.D., (1996) J. Chem. Soc. Dalton Trans., p. 739Weber, L., Sommer, O., Stammler, H.-G., Neumann, B., Kölle, U., (1995) Chem. Ber., 128, p. 665Ajulu, F.A., Bartsch, R., Carmichael, D., Johnson, J.A., Jones, C., Matos, R.M., Nixon, J.F., (1995) Phosphorus-31 NMR Spectral Properties in Compound Characterisation and Structural Analysis, pp. 229-242. , Eds Quin, L. D. and Vekade, J. G., VCH, Weinheim, ch. 18Braga, D., Grepioni, F., Byrne, J.J., Calhorda, M.J., (1995) J. Chem. Soc. Dalton Trans., p. 3287Besançon, K., Laurenczy, G., Lumini, T., Roulet, R., Gervasio, G., (1993) Helv. Chim. Acta, 76, p. 2926. , and references cited thereinLumini, T., Laurenczy, G., Roulet, R., Tassan, A., Ros, R., Schenck, K., Gervasio, G., (1998) Helv. Chim. Acta, 81, p. 781Churchill, M.R., Hutchinson, J.P., (1978) Inorg. Chem., 17, p. 3528Benvenutti, M.H.A., Vargas, M.D., Braga, D., Grepioni, F., Parisini, E., Mann, B.E., (1993) Organometallics, 12, p. 2955Ros, R., Scrivanti, A., Albano, V.G., Braga, D., Garlaschelli, L., (1986) J. Chem. Soc. DaltonTrans., p. 2411Detzel, M., Friedrich, G., Scherer, O.J., Wolmershäuser, G., (1995) Angew. Chem. Int. Ed. Engl., 34, p. 1321Ros, R., Scrivanti, A., Albano, V.G., Braga, D., Garlaschelli, L., (1986) J. Chem. Soc. DaltonTrans., p. 2411Laurenczy, G., Bondietti, G., Ros, R., Roulet, R., (1996) Inorg. Chim. Acta, 247, p. 65. , and references cited thereinBartsch, R., Hitchcock, P.B., Nixon, J.F., (1987) J. Chem. Soc. Chem. Commun., p. 1146Binger, P., Glaser, G., (1994) J. Organomet. Chem., 479, pp. C28Chini, P., Ciani, G., Garlaschelli, L., Manassero, M., Martinengo, S., Sironi, A., Canziani, F., (1978) J. Organomet. Chem., 152, pp. C3

Syntheses And Structural Characterisation Of [ir4(co)11(η1-l)] And [ir4(co)10(η1-l)2] {l = [fe(η5-p3c2but 2)(η5-p2c3but 3)] And [fe(η5-c5h5)...

Title full: Syntheses and structural characterisation of [Ir4(CO)11(η1-L)] and [Ir4(CO)10(η1-L)2] {L = [Fe(η5-P3C2But 2)(η5-P2C3But 3)] and [Fe(η5-C5H5)(η5-P 3C2But 2)]} and [Ir4(CO)11{μ-η1:η 1-[Fe(η5-C5H5)(η 5. The reactions of NBu4[Ir4(CO)11Br] 1 with equivalent amounts of [Fe(η5-P3C2But 2)(η5-P2C3But 3)] L1 or [Fe(η5-C5H5)(η5-P 3C2But 2)] L2 in the presence of AgSbF6 gave good yields of [Ir4(CO)11(η1-L)] 2a or 2b, besides [Ir4(CO)10(η1-L)2] 3a and 3b, respectively, in which the ligands are bound via the PA atom. The solid-state structure of 2b, established by an X-ray analysis, is that of the Td-like isomer, although the low-temperature 31P-{1H} NMR spectrum showed the presence of both C3v- and Td-like isomers in solution. Compound 2a underwent facile conversion to [Ir4(CO)10(μ-η2-L1)] 4a via CO loss and further interaction of the adjacent PB atom of L1. 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