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    National Tsing Hua University Institutional Repository > 理學院 > 化學系 > 期刊論文 >  Synthesis, characterization, and reaction chemistry of complexes of the molybdenum-pentadienyl-nitrogen ligand system. Molecular structure and reactivity of 16-electron syn-.eta.3-pentadienyl complexes

    Please use this identifier to cite or link to this item: http://nthur.lib.nthu.edu.tw/dspace/handle/987654321/57588

    Title: Synthesis, characterization, and reaction chemistry of complexes of the molybdenum-pentadienyl-nitrogen ligand system. Molecular structure and reactivity of 16-electron syn-.eta.3-pentadienyl complexes
    教師: 劉瑞雄
    Date: 1990
    Publisher: American Chemical Society
    Relation: Organometallics,American Chemical Society,Volume: 9,Issue: 6,Pages: 1862-1871,Published: JUN 1990
    Keywords: 16-electron syn-.eta.3-pentadienyl complexes
    Molecular structure
    molybdenum-pentadienyl-nitrogen ligand system
    Abstract: The reaction between MO(CO)~(CH~CN)~(~~-C~H~)B~ and 2,2'-bi yridine (bpy) or 1,lO-phenanthroline
    (phen) yields complexes of the type MO(CO)~(-)(TJ~-C~H~)B~ (d = bp (la), hen (lb)), res ectively. Treatment of la or lb with AgBF, in CHzClz respectively gives M O ( C O ) ~ ( ~ ) ( ~ ~ C ~ H ~ ) B F ~ (I" = bpy (2a), phen (2b)), in which the pentadienyl ligand adopts a syn-q3 configuration, whereas the BF4- anion serves as +coordinating ligand. In donor solvents such as CH3CN, THF, and acetone, 2a and 2b take up one solvent molecule to yield complexes of the type [Mo(C0),(Pfbl)(q3-C5H7)S]BF4 (m = bpy, S = CH3CN (3a), acetone (3b), ether (3c); Pfbl = phen, S = CH3CN (4a), acetone (4b), ether (4c)). For 3a and 4a, two conformers are isolable in equal proportions. A 'H spin saturation transfer experiment reveals that the two isomers undergo mutual exchange by rotation of the metal-allyl bond. For 3b,c, and
    4b,c, one extra pair of conformers was detected in addition to the isomers identical with those of 3a and 4a. The 16-electron compound M O ( C O ) ~ ( ~ ) ( ~ ~ - C ~ H ~ ) (5a; m = (C6H5)2B(p~)z, pz = pyrazolyl) has been synthesized from the reaction between N&(C6H5),(pz), and MO(CO)~(CH,CN)~(~~-C~H,)B~. The solid-state structure of 5a has been fully characterized. In solution, the molecule is stereochemically nonrigid. There is NMR evidence that shows the chemical exchange between the two inequivalent pyrazole and the two inequivalent phenyl groups. The fluxional mechanism proceeds with rotation of the chelate nitrogen ligand along the Mo-B axis. Complex 5a reacts with tertiary phosphines to produce the 18electron complexes MO(CO)~(~)(~~-C~H,)L (L = PMe, (6a), P(OPh)3 (6b)). The reaction between HzO and 5a gives [ (C6H5)zB(pz)(OH)Mo(q3-NNCHCHCHCH2CHCHCHCH3)] (7a) in moderate yield. Structural charac- terization of 7a was achieved by X-ray diffraction studies of its tungsten analogue 7b. Molecular structures of 3a, 5a, 6a, and 7b have been determined by X-ray diffraction with the following parameters: 3a, space
    group P1, a = 8.107 (4) A, b = 11.055 (3) i\, c = 13.118 (3) A, a = 106.42 (2)O, a= 95.39 (3)O, y = 96.41 (3)O, R = 4.0% and R, = 4.1% for 2624 reflections >3.0u(n; 5a, space group P1, a = 9.951 (13) A, b = 10.435 (7) A, c = 12.210 (8) A, (Y = 82.31 (SI0, B = 79.27 (9)O, y = 74.62 (lo)', R = 6.7% and R, = 7.4% for 2368 reflections >2.Ou(I); 6a, space group P2,/c, a = 14.552 (5) A, b = 9.7108 (23) A, c = 19.862 (8) A, /3 = 90.48 (3)O 2 = 4, R = 4.2% and R, = 3.6% for 1421 reflections >2.0u(I); 7b, space group P212121, a = 10.0979 (21) A, b = 13.6753 (23) A, c = 17.331 (3) A, 2 = 4, R = 3.2% and R, = 2.7%, for 2650 reflections >2.0u(r).
    URI: http://pubs.acs.org/
    Appears in Collections:[化學系] 期刊論文

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