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Cyanide Compounds
No full textChapter 4, “Cyanide Compounds,” illustrates an explosively developing research theme in which the cyanide ligand is used as a linking agent for the designed assembly of polynuclear metal complexes. Syntheses of several basic building blocks, such as K3[Cr(CN)6],Cr(Me3tacn)(CN)3,K4[Mo(CN)8],Na[W(CO)5CN],K[CpFe(CO)(CN)2],[NEt4][Cp*Rh(CN)3],[Fe4(bpy)8(μ-CN)4][PF6]4,. are given here. These units may be used in several ways to construct polynuclear compounds. One approach involves a hexacyanometalate core decorated with peripheral metal centers, e.g., [{Cu(tpa)(CN)}6Fe][ClO4]8. or [Cr{CNNi(tetren)}6][ClO4]9. An octacyanometalate unit can lead to higher nuclearity condensed compounds, as in [Co{Co(MeOH)3}8(μ-CN)30{Mo(CN)3}6]. Alternatively, a cluster core may be substituted with cyano complexes as ligands, as in [PPh4]2[Fe4S4{NCW(CO)5}4]. If there are two cis cyano ligands on the building block, then quadrilateral or square structures often result, as in {CpFe(CO(μ-CN)2Cu(PCy3)}2 and [Fe2Cu2(bpy)6(μ-CN)4][PF6]4 However, if there are three adjacent cyano ligands, then cubic cages may be constructed as in [(CpCo)4(Cp*Rh)4(μ-CN)12][PF6]4
Synthesis and reactivity studies of high-nuclearity carbido carbonyl clusters of heptarhenium-iridium and decaruthenium
No full textThe cluster anion (\rm Re\sb7C(CO)\sb{21}Ir(C\sb8H\sb{14})(CO)\rbrack \sp{2-} has been synthesized by the capping of (\rm Re\sb7C(CO)\sb{21}\rbrack \sp{3-} with the in-situ generated cationic species from the reaction of (\rm Ir(C\sb8H\sb{14})\sb2(CO)Cl\rbrack \sb2 and AgBF\sb4. This new heptarhenium-iridium compound reacts with two electron donors to give ligand-substituted compounds (\rm Re\sb7C(CO)\sb{21}Ir(L)(CO)\rbrack \sp{2-} (L = CO, \rm C\sb2H\sb4, PMePh\sb2, and PPh\sb3), and with triphenylsilane and allyl bromide to form the oxidative addition products (\rm Re\sb7C(CO)\sb{21}Ir(H)(CO)(SiPh\sb3)\rbrack \sp{2-} and (\rm Re\sb7C(CO)\sb{21}Ir(\eta\sp3C\sb3H\sb5)(CO)\rbrack \sp-. The reactivities at iridium parallel those of the indenyl complex \rm (\eta\sp5C\sb9H\sb7)Ir(C\sb8H\sb{14})(CO), thus giving further support for the previously proposed analogy between (\rm Re\sb7C(CO)\sb{21}\rbrack \sp{3-} and the cyclopentadienyl ligand and its derivatives. Formulation and characterization of these new compounds are based on elemental analysis, IR, \sp1H and \sp{13}C NMR spectroscopies, fast-atom bombardment mass spectrometry, and X-ray crystallography.The cluster anion (\rm Re\sb7C(CO)\sb{21}Ir(CO)\sb2\rbrack \sp{2-} undergoes an irreversible framework isomerization process in solution to form a new isomer \rm \{\lbrack Re(CO)\sb3\rbrack\sb2\lbrack Re\sb5IrC(CO)\sb{17}\rbrack \}\sp{2-}. Kinetic studies have been carried out, and a reaction mechanism has also been proposed. In refluxing acetonitrile \rm \{\lbrack Re(CO)\sb3\rbrack\sb2\lbrack Re\sb5IrC(CO)\sb{17}\rbrack \}\sp{2-} loses a Re(CO)\sb3\sp+ fragment, leading to the formation of \rm \lbrack Re\sb6IrC(CO)\sb{20}\rbrack \sp{3-}. This analog of \rm \lbrack Re\sb7C(CO)\sb{21}\rbrack \sp{3-} reacts with Au(PPh\sb3)Cl to give (\rm Re\sb6IrC(CO)\sb{20}Au(PPh\sb3)\rbrack \sp{2-} and \rm \{Re\sb6IrC(CO)\sb{20}\lbrack Au(PPh\sb3)\rbrack \sb2\}\sp-, which have been characterized by \sp{31}P and \sp{13}C NMR studies.The known cluster anion (\rm Ru\sb{10}C\sb2(CO)\sb{24}\rbrack \sp{2-} can be prepared via an alternative route involving the redox condensation of (\rm Ru\sb6C(CO)\sb{16}\rbrack \sp{2-} and Ru\sb5C(CO)\sb{15}. Substitution of two apical carbonyls in (\rm Ru\sb{10}C\sb2(CO)\sb{24}\rbrack \sp{2-} by one diphenylacetylene molecule gives the compound (\rm Ru\sb{10}C\sb2(CO)\sb{22}(C\sb2Ph\sb2)\rbrack \sp{2-}, which contains a new ruthenium-ruthenium bond between the two apical atoms in the bioctahedral structure. Carbonyl ligand dynamic exchange behavior has been observed by variable-temperature \sp{13}C NMR spectroscopy.Made available in DSpace on 2011-05-07T13:51:40Z (GMT). No. of bitstreams: 2
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Previous issue date: 1991Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding ([email protected]) on 2011-05-07T15:00:02Z
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The 'Indenyl Effect' in iridium(I) olefin complexes
No full text"The complexes CpIr(\eta\sp2-C\sb8H\sb{14})CO and (\eta\sp5-C\sb9H\sb7)Ir(\eta\sp2-C\sb8H\sb{14})CO were prepared in high yield from ((\eta\sp2-C\sb8H\sb{14})\sb2Ir(CO)Cl) \sb2 and thallium cyclopentadienide or potassium indenide, respectively. The stereoisomers of CpIr(\eta\sp2-C\sb8H\sb{14})CO, (\eta\sp5-C\sb9H\sb7)Ir(\eta\sp2-C\sb8H\sb{14})CO, and (\eta\sp5-C\sb9H\sb7)Ir(\eta\sp2-C\sb8H\sb{14})\sb2, were characterized by two-dimensional NMR techniques. Due to the ""Indenyl Effect,"" (\eta\sp5-C\sb9H\sb7)Ir(\eta\sp2-C\sb8H\sb{14})CO was more reactive than CpIr(\eta\sp2-C\sb8H\sb{14})CO toward Lewis bases. The labile cyclooctene ring of (\eta\sp5-C\sb9H\sb7)Ir(\eta\sp2-C\sb8H\sb{14})CO was readily replaced under mild conditions by other two electron donors such as triphenylphosphine, carbon monoxide, ethylene, or phenylacetylene; CpIr(\eta\sp2-C\sb8H\sb{14})CO was not reactive under identical or more severe conditions. The complex (\eta\sp5-C\sb9H\sb7)Ir(\eta\sp2-C\sb8H\sb{14})CO readily oxidatively added C-Br and Si-H bonds, again under mild conditions, and was found to be an active and robust catalyst for the hydrogenation and hydrosilylation of alkenes and alkynes. The reaction of CO with (\eta\sp5-C\sb9H\sb7)Ir(CO)\sb2 resulted in the formation of the \eta\sp1-slipped indenyl ring of (\eta\sp1-C\sb9H\sb7)Ir(CO)\sb3.""For CpIr(\eta\sp2-C\sb2H\sb4)L and (\eta\sp5-C\sb9H\sb7)Ir(\eta\sp2-C\sb2H\sb4)L, where L = ethylene or CO, the barrier to ethylene rotation about the iridium-ethylene bond axis was determined by lineshape fitting of variable-temperature \sp1H NMR spectra. The free energies of activation were found to be 5-6 kcal/mole less for the indenyl complexes than for the corresponding cyclopentadienyl complexes (14 and 20 kcal/mole, respectively). This lowering of the barrier to ethylene rotation is an attribute of the ""Indenyl Effect."""Some related projects included the following. Attempted preparation of CpIr(\eta\sp2-C\sb8H\sb{14})\sb2 resulted in an unexpected but useful synthesis of the cyclopentadiene complex CpIr(\eta\sp4-C\sb5H\sb6). The proton and carbon resonances of the series of complexes CpM(\eta\sp4-C\sb5H\sb6), where M = Co, Rh, or Ir, were compared. Protonation studies of CpIr(\eta\sp2-C\sb8H\sb{12}) and (\eta\sp5-C\sb9H\sb7)Ir(\eta\sp2-C\sb8H\sb{12}) allowed us to examine \eta\sp5 to \eta\sp6 haptotropic indenyl ring shifts. Synthetic routes to a metal cyclopentaphenanthrene complex Cp*Ru(\eta\sp5-C\sb{15}H\sb9), were explored.Made available in DSpace on 2011-05-07T12:51:59Z (GMT). No. of bitstreams: 2
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Heterogeneous catalytic studies with rhenium cluster-based precursors
No full textWhen (Re(CO)\sb3OH) \sb4 was supported on Al\sb2O\sb3 followed by heating in H\sb2 no decomposition gas products, CO and CH\sb4, were observed below 650 K. Following the activation by infrared spectroscopy showed the formation of Re(CO)\rm\sb3\{O--Al\}\sb2 at 480 K. The activated sample, (Re\sb4) /Al\sb2O\sb3, when exposed to CO/H\sb2 at 298 K, produced CH\sb4 near 500 K with a shoulder near 600 K in the temperature programmed reaction (TPR) profile. Elevating the CO/H\sb2 treatment temperature to 500 K resulted in the formation of CH\sb4 at 560 K. The adsorption of CH\sb3OH or CH\sb3I to the sample produced CH\sb4 at 580 K. When (Re(CO)\sb3OH) \sb4 activated on SiO\sb2, only one CH\sb4 peak at 490 K was observed for CO/H\sb2 adsorption. When TiO\sb2 was used as a support, a spillover species was also observed from CO and H\sb2 exposure at 500 K. The spillover rate appeared to be slower on TiO\sb2 than was observed on Al\sb2O\sb3.When both the PPN\sp+ and Et\sb4N\sp+ forms of (Re\sb7IrC(CO)\sb{23}\rbrack\sp{2-} and (Re\sb5IrC(CO)\sb{17}\{Re(CO)\sb3\}\sb2\rbrack\sp{2-} were supported on Al\sb2O\sb3, their decompositions were followed by TPDE and infrared spectroscopy. For the hydrogenolysis of ethane, the most and least active catalyst samples were (Re\sb7Ir(Et\sb4N)) /Al\sb2O\sb3, and (ReIr\sb7(PPN)) /Al\sb2O\sb3, respectively. The other two samples, (Re\sb5IrRe\sb2(Et\sb4N)) /Al\sb2O\sb3 and (Re\sb5IrRe\sb2(PPN)) /Al\sb2O\sb3, showed comparable activity. All samples appeared, by infrared spectroscopy, to form Re(CO)\sb3\{O-AlHO-Al\}\sb2 and smaller nuclearity clusters on the surface during decomposition. The amount of Re(CO)\sb3\{O-AlHO-Al\}\sb2 formed at 573 K correlated with the ethane hydrogenolysis activity of the resulting catalyst. The sample most active for ethane hydrogenolysis, (Re\sb7Ir(Et\sb4N)) /Al\sb2O\sb3, produced the largest amount of Re(CO)\sb3\{O-AlHO-Al\}\sb2during activation by 573 K, 60% of the available rhenium, and the sample least active, (Re\sb7IrC(CO)\sb{23}(PPN)) /Al\sb2O\sb3, resulted in the smallest amount, 40%. All samples produced CH\sb4 in the TPR profiles from the adsorption of CO in H\sb2.Made available in DSpace on 2011-05-07T12:59:50Z (GMT). No. of bitstreams: 2
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Previous issue date: 1995Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding ([email protected]) on 2011-05-07T14:48:49Z
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Substitution and redox reactions of heptarhenium cluster derivatives
No full textThe second-order rate constants for the reactivity of (Re\sb7C(CO)\sb{21}Rh(CO)\sb2) \sp{2-} towards phosphorus donors were determined. In order to correlate the results to electronic and/or steric effects, steric profiles relating log k\sb2 to an intrinsic reactivity an electronic parameter and a steric parameter were constructed. From differences in intrinsic reactivity for phosphines and phosphites, an intermediate configuration involving a bridging carbonyl has been proposed for the reaction of (Re\sb7C(CO)\sb{21}Rh(CO)\sb2) \sp{2-} with various phosphorus donors (PY\sb3).Nitrosylation of a series of mixed-metal heptarhenium clusters, (Re\sb7C(CO)\sb{21}ML\sb{\rm n}) \sp{2-}, gave the mono-substituted products, (Re\sb7C(CO)\sb{20}ML\sb{\rm n}\rbrack\sp-. A variety of spectroscopic techniques were used to characterize the reaction products. Variable temperature \sp{13}C NMR studies determined the solution structure of (Re\sb7C(CO)\sb{20}(NO)Rh(CO)\sb2) \sp-. From kinetic studies, the nitrosyl substituted cluster (Re\sb7C(CO)\sb{20}(NO)Rh(CO)\sb2) \sp- exhibits enhanced reactivity toward phosphorus ligands in comparison with (Re\sb7C(CO)\sb{21}Rh(CO)\sb2) \sp{2-}.The carbonyl ligands bound to (Re\sb7C(CO)\sb{21}Rh(CO)\sb2) \sp{2-} display unusual intermolecular and intramolecular exchange. Upon treatment with \sp{13}CO, (Re\sb7C(CO)\sb{21}Rh(CO)\sb2) \sp{2-} is selectively \sp{13}CO enriched to (\rm Re(CO)\sb3Re\sb6C(\sp{13}CO)\sb{18}Rh(\sp{13}CO)\sb2\rbrack \sp{2-}. A capping Re(CO)\sb3 moiety trans to the rhodium cap remains unenriched. Formation of the radical species (Re\sb7C(CO)\sb{21}Rh(CO)\sb2\rbrack\sp- by chemical oxidation results in complete carbonyl scrambling, which is revealed upon reduction to the parent cluster (\rm Re(\sp{13}CO)\sb3Re\sb6C(\sp{13}CO)\sb{18}Rh(\sp{13}CO)\sb 2\rbrack \sp{2-}. The selectively \sp{13}Co enriched cluster (Re(CO)\sb3Re\sb6C(\sp{13}CO)\sb{18}) \sp{2-} has been formed in a decapping reaction of (\rm Re(CO)\sb3Re\sb6C(\sp{13}CO)\sb{18}Rh(\sp{13}CO\sb2\rbrack \sp{2-} with excess PPh\sb3 in acetonitrile.Two-electron oxidation of (Re\sb7C(CO)\sb{21}) \sp{3-} in the presence of P(OPh)\sb3 affords (Re\sb7C(CO)\sb{21}(P(OPh)\sb3)) \sp-. \sp{13}C NMR indicates that this cluster exhibits partial charge separation. (Re\sb7C(CO)\sb{21}(P(OPh)\sb3)) \sp- decomposes in acetonitrile to form (Re\sb6C(CO)\sb{19}) \sp{2-} and (Re(CO)\sb3(P(OPh)\sb3)\sb2(NCCH\sb3)) \sp+, and therefore it represents a directly observed intermediate in a cluster decapping reaction.Made available in DSpace on 2011-05-07T12:36:21Z (GMT). No. of bitstreams: 2
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Previous issue date: 1991Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding ([email protected]) on 2011-05-07T14:43:13Z
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Multinuclear NMR studies on solution structures and dynamics of triosmium hydrido carbonyl phosphine cluster compounds
No full textThe reaction of (-H)\sb2Os\sb3(CO)\sb9(PPh\sb3) with acetylene at room temperature provides two isomers of a hydridovinyl cluster. The solid-state structure of each isomer has been determined by single-crystal X-ray crystallography. The solution structures and dynamics have been studied by extensive \sp{13}C NMR studies, including \sp{13}C\{\sp1H COSY and \sp{13}C spin saturation transfer experiments.\sp1H and \sp{13}C NMR studies show that the reaction of (-H)\sb2Os\sb3(CO)\sb9(PPh\sb3) with ethylene gives (-H)\sb2Os\sb3(CO)\sb9(PPh\sb3)(-CHCH\sb3), instead of the previously formulated complex (-H)(H)Os\sb3(CO)\sb9(PPh\sb3)(C\sb2H\sb4).The reaction of (-H)\sb2Os\sb3(CO)\sb9(PMe\sb2Ph) with Bu\sp{\rm t}NC produces two pairs of two isomers of an isonitrile cluster, (-H)(H)Os\sb3(CO)\sb9(PMe\sb2Ph)(Bu\sp{\rm t}NC). The origin, structure, and dynamic behavior of these isomers have been investigated by \sp1H, \sp{13}C, and \sp{31}P NMR studies.The reaction of (-\rm H)\sb2Os\sb3(CO)\sb9(PPh\sb3) with ethereal diazomethane in chloroform gives a novel compound, ((-H)\sb2Os\sb3(CO)\sb8(PPh\sb3)\sb2) \sb2(-cis-CHCH=CHCH\sb2CH), in which two triosmium carbonyl units are connected through a hydrocarbon fragment. This formulation is based on data obtained from mass spectrometry, elemental analysis, and extensive \sp1H, \sp{13}C, and \sp{31}P NMR studies.A combination of \sp{13}C\{\sp1H COSY, selectively \sp1H decoupled \sp{13}C NMR, and \sp{13}C spin saturation transfer experiments on the pair of tautomers, (-H)Os\sb3(*CO)\sb{10}(-CH\sb3)/(-H)\sb2Os\sb3(*CO)\sb{10}(-CH\sb2) has established the overall solution dynamics of these compounds.Made available in DSpace on 2011-05-07T13:49:42Z (GMT). No. of bitstreams: 2
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Previous issue date: 1991Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding ([email protected]) on 2011-05-07T14:59:38Z
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Synthesis and reactivity studies of rhenium carbido carbonyl cluster compounds
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Previous issue date: 1994Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding ([email protected]) on 2011-05-07T15:01:31Z
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Reason: ETDs are only available to UIUC Users without author permissionTreatment of \rm\lbrack Re\sb7C(CO)\sb{21}\rbrack\sp{3-} with PPh\sb3 in the presence of two equivalents of \rm\lbrack Cp\sb2Fe\rbrack\sp+ under a CO atmosphere provided \rm\lbrack Re\sb6C(CO)\sb{19}\rbrack\sp{2-}. X-ray diffractional studies and \sp{13}C NMR studies on \rm\lbrack Re\sb6C(CO)\sb{19}\rbrack\sp{2-} showed a congested ligand environment. Sunlamp irradiation of \rm\lbrack Re\sb6C(CO)\sb{19}\rbrack\sp{2-} in the presence of H\sb2 gave \rm\lbrack H\sb2Re\sb6C(CO)\sb{18}\rbrack\sp{2-}.Treatment of \rm \lbrack PPN\rbrack\sb3\lbrack Re\sb7C(CO)\sb{21}\rbrack with two equivalents of \rm\lbrack Cp\sb2Fe\rbrack\sp+ in the presence of diazomethane gave (PPN) (Re\sb7C(CO)\sb{21}(CH\sb2)). Treatment of \rm\lbrack Re\sb7C(CO)\sb{21}(CH\sb2)\rbrack\sp- with acetonitrile gave \rm\lbrack Re\sb6C(CO)\sb{18}(CH\sb2)\rbrack\sp{2-}. The methylene ligand in \rm\lbrack Re\sb7C(CO)\sb{21}(CH\sb2)\rbrack and \rm\lbrack Re\sb6C(CO)\sb{18}(CH\sb2)\rbrack\sp{2-} is found bridging a rhenium-rhenium edge. The syntheses of other \rm\lbrack Re\sb7C(CO)\sb{21}L\rbrack\sp- and \rm \lbrack Re\sb6C(CO)\sb{18}L\rbrack\sp{2-} compounds are also discussed.The reaction of \rm\lbrack PPN\rbrack\sb2\lbrack Re\sb6C(CO)\sb{19}\rbrack with Mo(CO)\sb6 and \rm Ru\sb3(CO)\sb{12} under photolytic conditions gave \rm \lbrack PPN\rbrack\sb2\lbrack Re\sb6C(CO)\sb{18}Mo(CO)\sb4\rbrack and \rm \lbrack PPN\rbrack\sb2\lbrack Re\sb6C(CO)\sb{18}Ru(CO)\sb3\rbrack, respectively. A comparison of the physical properties and reactivity of \rm \lbrack PPN\rbrack\sb2\lbrack Re\sb6C(CO)\sb{18}Mo(CO)\sb4\rbrack and \rm\lbrack PPN\rbrack\sb2\lbrack Re\sb6C(CO)\sb{18}Ru(CO)\sb3\rbrack is described.The reaction of either \rm\lbrack H\sb2Re\sb6C(CO)\sb{18}\rbrack\sp{2-} or \rm\lbrack HRe\sb6C(CO)\sb{18}\rbrack\sp{3-} with (AuPPh\sb3)Cl in the presence of DBU gave \rm\lbrack Re\sb6C(CO)\sb{18}(AuPPh\sb3)\sb2\rbrack\sp{2-}. \rm\lbrack Re\sb6C(CO)\sb{18}(AuPPh\sb3)\sb2\rbrack\sp{2-} reacted with (AuPPh\sb3)NO\sb3 to give \rm\lbrack Re\sb6C(CO)\sb{18}(AuPPh\sb3)\sb4\rbrack. \rm \lbrack Re\sb6C(CO)\sb{18}(AuPPh\sb3)\sb2\rbrack\sp{2-} also reacted with \rm\lbrack Rh(CO)\sb2Cl\rbrack\sb2 to give \rm \lbrack Re\sb6C(CO)\sb{18}(AuPPh\sb3)\sb2Rh(CO)\sb2\rbrack\sp-. Synthesis of other \rm \lbrack Re\sb6C(CO)\sb{18}ML\sb{n}\rbrack\sp{3-} complexes will also be discussed.Treatment of \rm\lbrack Re\sb7C(CO)\sb{21}\rbrack\sp{3-} with one equivalent of \rm\lbrack Cp\sb2Fe\rbrack\sp+ gave the \rm\lbrack Re\sb7C(CO)\sb{21}\rbrack\sp{2-} radical, and introduction of tributyltin hydride or a silane gave \rm\lbrack HRe\sb7C(CO)\sb{21}\rbrack\sp{2-}. The \rm \lbrack Re\sb7C(CO)\sb{21}\rbrack\sp{2-} radical also reacted with solvents such as acetone or THF, giving \rm\lbrack HRe\sb7C(CO)\sb{21}\rbrack\sp{2-}. The nature of the counter ion in the cluster compound and the \rm\lbrack Cp\sb2Fe\rbrack\sp+ oxidant also played a role in the reactivity.ETDs are only available to UIUC Users without author permissionU of I Onl
Synthesis and properties of mononuclear and polynuclear indenyl iridium complexes
No full textThe reaction of \rm Ir(CO)\sb2(\eta\sp5-\rm C\sb9H\sb7) with \rm Ir(\eta\sp2-\rm C\sb2H\sb4)\sb2(\eta\sp5-\rm C\sb9H\sb7) provided \rm Ir\sb3(\mu-\rm CO)\sb3(\eta\sp5-\rm C\sb9H\sb7)\sb3, and the reaction of \rm Ir(CO)\sb2(\eta\sp5-\rm C\sb9H\sb7) with \rm Rh(\eta\sp2-\rm C\sb2H\sb4)\sb2(\eta\sp5-\rm C\sb9H\sb7) provided \rm Ir\sb{3-x}Rh\sb{x}(\mu-\rm CO)\sb3(\eta\sp5-\rm C\sb9H\sb7)\sb3 (x = 0 - 3) in good yields. These compounds react readily with carbon monoxide or PPh\sb3 at room temperature to form mononuclear products.The reaction of \rm Ir\sb3(CO)\sb3(\eta\sp5-\rm C\sb9H\sb7)\sb3 with HBF\rm\sb4\cdot Et\sb2O gave \rm\lbrack Ir\sb3(\mu-\rm H)(CO)\sb3(\eta\sp5-\rm C\sb9H\sb7)\sb3\rbrack\lbrack BF\sb4). Subsequent deprotonation led to generation of \rm C\sb{S}-\rm Ir\sb3(CO)\sb3(\eta\sp5-\rm C\sb9H\sb7)\sb3, which rapidly reverted to an equilibrium mixture containing major isomer \rm C\sb{3v}-\rm Ir\sb3(\mu-\rm CO)\sb3(\eta\sp5-\rm C\sb9H\sb7)\sb3 and minor isomer \rm C\sb{S}-\rm Ir\sb3(CO)\sb3(\eta\sp5-\rm C\sb9H\sb7)\sb3. Variable temperature NMR experiments indicated that \rm C\sb{S}-\rm Ir\sb3(CO)\sb3(\eta\sp5-\rm C\sb9H\sb7)\sb3 undergoes a dynamic process that involves a third isomer of \rm Ir\sb3(CO)\sb3(\eta\sp5-\rm C\sb9H\sb7)\sb3. This study provides a unique set of relative energies in solution for three of the four observed forms for a \rm M\sb3(CO)\sb3(\eta\sp5-\rm L)\sb3 system.The reactions of \rm C\sb{3v}-\rm Ir\sb3(\mu-\rm CO)\sb3(\eta\sp5-\rm C\sb9H\sb7)\sb3 with metal fragment electrophiles containing Cu, Ag, Au, or Hg provided cationic tetranuclear clusters, which show a rearrangement of the \rm Ir\sb3(\eta\sp5-\rm C\sb9H\sb7)\sb3 moiety to a \rm C\sb{S} geometry. The reaction with TIPF\sb6 gave \rm\lbrack Ir\sb3Tl(\mu-\rm CO)\sb3(\eta\sp5-\rm C\sb9H\sb7)\sb3\rbrack\lbrack PF\sb6), which maintains \rm C\sb{3v} geometry and has the thallium ion encapsulated by the six-membered rings of the indenyl ligands.The reaction of \rm Ir(CO)(\eta\sp2-\rm C\sb8H\sb{14})(\eta\sp5-\rm C\sb9H\sb7) with \rm Re\sb2(\mu-\rm H)\sb2(CO)\sb8 formed the mixed-metal cluster \rm IrRe\sb2(\mu-\rm H)\sb2(CO)\sb9(\eta\sp5-\rm C\sb9H\sb7). Deprotonation with KOH/EtOH and addition of (PPN) (Cl) provided \rm\lbrack PPN\rbrack\lbrack IrRe\sb2(\mu-\rm H)(CO)\sb9(\eta\sp5-\rm C\sb9H\sb7)). Addition of PPh\sb3 to \rm IrRe\sb2(\mu-\rm H)\sb2(CO)\sb9(\eta\sp5-\rm C\sb9H\sb7) led to the carbonyl substitution product \rm IrRe\sb2(\mu-\rm H)\sb2(CO)\sb8(PPh\sb3)(\eta\sp5-\rm C\sb9H\sb7), which contains the phosphine ligand on a rhenium atom, as well as to cluster fragmentation.The reactions of \rm Ir(CO)(\eta\sp2-\rm C\sb8H\sb{14})(\eta\sp5-\rm C\sb9H\sb7) with \rm C\sb2R\sb2 led to \rm Ir(CO)(\eta\sp2-\rm C\sb2R\sb2)(\eta\sp5-\rm C\sb9H\sb7) and \rm Ir\sb2(CO)\sb2(\mu-\rm C\sb2R\sb2)(\eta\sp5-\rm C\sb9H\sb7)\sb2 (R = Ph, Tol). Also, alkyne coupling and activation of a C-H bond in the arene solvent formed a novel mononuclear compound containing a substituted butadiene ligand.Made available in DSpace on 2011-05-07T12:30:24Z (GMT). No. of bitstreams: 2
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Previous issue date: 1996Item marked as restricted to the 'UIUC Users [automated]' Group (id=2) by Howard Ding ([email protected]) on 2011-05-07T14:41:54Z
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Reason: ETDs are only available to UIUC Users without author permissionETDs are only available to UIUC Users without author permissionU of I Onl
Synthesis and Characterization of Mononuclear and Polynuclear Metal-Fullerene Complexes
No full text129 p.Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1997.The reaction of \rm Ru\sb6C(CO)\sb{17} with C\sb{60} followed by carbonyl substitution with bis(diphenylphosphino)methane gave \rm Ru\sb6C(CO)\sb{12}(dppm)(\mu\sb3-\eta\sp2,\eta\sp2,\eta \sp2-C\sb{60}). A related arene-Ru\sb6C compound, \rm Ru\sb6C(CO)\sb{13}\{PPh\sb2(\mu-\eta\sp6-\rm C\sb6H\sb6)\}, was obtained by thermolysis of \rm Ru\sb6C(CO)\sb{16}PPh\sb3, in which the tendency of the Ru\sb6C framework to form arene complexes is extend to a coordinated triphenylphosphine moiety, leading to (reversible) coordination of a phenyl ring to an adjacent ruthenium center in the cluster unit.U of I OnlyRestricted to the U of I community idenfinitely during batch ingest of legacy ETD
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