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de Montigny F Macias R Noll BC Fehlner TP Costuas K Saillard JY Halet JF 《Journal of the American Chemical Society》2007,129(11):3392-3401
Building on earlier work that showed the formation of [1-Cp*-2,2,2-(CO)3-2-THF-nido-1,2-IrMoB(4)H(8)], 2, from the reaction of [1-Cp*-arachno-1-IrB(4)H(10)], 1, with (arene)Mo(CO)3, the stoichiometric mechanism for the generation of [1-Cp*-5,6,7,8-(R)4-nido-1,5,6,7,8-IrC(4)B(3)H(3)], 8, from the reaction of 2 with RCCR, R = Me, Ph, has been identified. For R = Me, the major product in solution is [1-Cp*-5,6,7,8-(CH3)4-closo-1,5,6,7,8-IrC(4)B(3)H(3)Mo(CO)3], 7, which is in equilibrium with 8. The equilibrium 8 + Mo(THF)3(CO)3 <==> 7 + 3THF is characterized by DeltaH = 8 kcal/mol and DeltaS = 34 cal/mol K. Density functional theory calculations carried out on 7 indicate that the Mo(CO)3 moiety is weakly bound to the cluster mainly through Mo-C rather than Mo-B interactions. Under alkyne deficient conditions, the product [1-Cp*-2,2,2-(CO)3(mu-CO)-3,4-(CH3)2-closo-1,2,3,4-IrMoC(2)B(3)H(3)], 6, can be isolated. Solid-state structures of 1 and 2 have been reported previously, and those of 6, 7, and 8, R = Me, Ph, are reported here. The evolution of products with time was monitored by 1H and 11B NMR and showed the formation and decay of two additional species which have been identified as the structural isomers [1-Cp*-7,7,7-(CO)3-7-THF-2,3-(CH3)2-nido-1,7,2,3-IrMoC(2)B(3)H(5)], 4, and [5-Cp*-7,7,7-(CO)3-7-THF-2,3-(CH3)2-nido-5,7,2,3-IrMoC(2)B(3)H(5)], 5, with the metals nonadjacent in 4 and adjacent in 5. Circumstantial evidence suggests that 4 is the precursor to 5 and 5 is the precursor to both 6 and 7. Cluster 2 also is a catalyst or catalyst precursor for the isomerization of olefins, namely, hex-1-ene to cis-hex-2-ene and tetramethyl allene to 2,4-dimethylpenta-1,3-diene. These novel results also establish that [1-Cp*-2,2,2-(CO)3-2-(alkyne)-nido-1,2-IrMoB(4)H(8)], 3, forms from 2 and constitutes a logical precursor to 4. The entire process, 1 + 2alkyne = 8 + BH3 + 2H2, which is promoted by (arene)Mo(CO)3, constitutes an explicit example of a transition-metal-facilitated process analogous to metal-facilitated organic transformations observed in organometallic chemistry. 相似文献
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Hong Yan Alicia M. Beatty Thomas P. Fehlner 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2001,113(23):4630-4633
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This work reports the results of a thermally driven cluster expansion of arachno-1-{eta5-C5Me5IrH2}B3H7, 1, with BH3.THF. In addition to the previously reported product, arachno-1-{eta5-C5Me5IrH}B4H9, 2, formed at lower temperatures, reaction at 100 degrees C permits the isolation of four new iridaboranes. Two products, nido-1-(eta5-C5Me5Ir)B5H9, 3, and nido-3-(eta5-C5Me5Ir)B9H13, 4, contain a single Ir atom and five and nine framework boron atoms, respectively. One, nido-3,4-(eta5-C5Me5Ir)2B8H12, 5, contains two Ir atoms and eight framework boron atoms. Their structures are predicted by the electron counting rules to be a nido-iridahexaborane, 3, nido-iridadecaborane, 4, and nido-diiridadecaborane, 5. The accuracy of these predictions in each case is established experimentally by spectroscopic characterization in solution and structure determinations in the solid state. A less stable metallaborane has been identified and the available spectroscopic and crystallographic information are consistent with the formulation nido-3,4-(eta5-C5Me5Ir)2B8H13(eta-BH2), 6, i.e., a species containing an exopolyhedral bridging BH group. These new observations, along with earlier ones on ruthenaborane cluster systems, are used to fully define a general mechanism for a cluster expansion reaction, i.e., addition of borane to form an exopolyhedral adduct followed by cage insertion. 相似文献
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We present several sets of special directions for integration over solid angle of functions with full cubic symmetry which represent a major advance in precision and thus can be applied to problems which are beyond the scope of present techniques. For example, it is possible to determine the first eight moments of a Fermi surface accurately from measurements along only ten special directions. 相似文献
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Ghosh S Shang M Li Y Fehlner TP 《Angewandte Chemie (International ed. in English)》2001,40(6):1125-1128
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The reaction of W(2)(OOCCF(3))(4) with (CO)(9)Co(3)CCOOH and Na[OOCCF(3)] in a nonpolar solvent mixture leads to the formation of the cluster of clusters {[Na][W(2){OOCCCo(3)(CO)(9)}(2)(OOCCF(3))(4)(THF)(2)]}(2), 1, in 40% yield. The structure of 1.3C(6)H(5)CH(3) in the solid state corresponds to a dimer of W(2) dinuclear complexes (monoclinic P2(1)/c, a = 15.234(6) ?, b = 23.326(11) ?, c = 20.658(7) ?, beta = 102.46(3) degrees; V = 7,168(5) ?(3); Z = 4; R(F)() = 8.39%). Each W(2) unit is bridged by two cis cluster carboxylates, and the remaining four equatorial sites are occupied by monodentate [OOCCF(3)](-) ligands. The axial positions contain coordinated THF. The W(2) carboxylate is opened up (W-W distance of 2.449(2) ?) so that the free ends of the [OOCCF(3)](-) ligands on both W(2) carboxylate units can cooperate in chelating two Na(+) ions thereby forming a dimer of W(2) complexes. A distinctive EPR spectrum with g = 2.08 is consistent with each W(2) carboxylate being a mixed-valent W(II)-W(III) species. The reaction of W(2)(OOCCF(3))(4) with (CO)(9)Co(3)CCOOH in THF in the absence of Na[OOCCF(3)] leads to the expected diamagnetic W(II)-W(II) cluster carboxylate W(2){OOCCCo(3)(CO)(9)}(3)(OOCCF(3))(THF)(2), 3. 相似文献