Crystal and molecular structure of .mu.-hydroxo-.mu.-di(p-tolyl)phosphido-hexacarbonyldiiron, Fe2(CO)6[P(p-C6H4CH3)2]OH

Treichel, P. M.; Dean, Walter K.; Calabrese, Joseph C.

doi:10.1021/ic50130a033

Cited by 33 publications

(10 citation statements)

References 15 publications

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“…The blue-shift of the -NC stretching mode of the -NC adsorbed at the top site compared to the ''free''-NC and strong substrate dependent peak position of the ''bonded''-NC peaks can be understood by considering the fact that the lone pair electrons of carbon atom of -NC group have antibonding character. 46 Donation of these electrons to a metal should increase the strength of -NC bond, resulting in the blue-shift of the peak position. The peak shift of the ''metal bonded (top)'' -NC to higher frequency is in the order of Pt o Ag o Au.…”

Section: Resultsmentioning

confidence: 99%

Substrate dependent structure of adsorbed aryl isocyanides studied by sum frequency generation (SFG) spectroscopy

Ito

Noguchi

Ikeda

et al. 2010

Phys. Chem. Chem. Phys.

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Effects of metal substrate on the bonding nature of isocyanide group of two aryl isocyanides, 1,4-phenylene diisocyanide (PDI) and 4-methylphenyl isocyanide (MPI), and tilt angle of MPI were examined by measuring sum frequency generation (SFG) spectra of the self-assembled monolayers (SAMs) of these molecules on Au, Pt, Ag, and Pd surfaces. The SFG peaks due to "metal bonded" and "free"-NC groups were resolved by comparing the SFG spectra of PDI with IR spectra obtained by DFT calculations and previous results of vibrational spectroscopy. Based on the peak positions of the "metal bonded"-NC, it is clarified that while PDI and MPI were adsorbed at top sites on Au, Ag, and Pt surfaces, they adsorbed at bridge sites on the Pd surface. The tilt angles of MPI were determined from the intensity ratio between the SFG peaks of C-H symmetric and asymmetric stretching vibrational modes of the CH(3) group. The tilt angles of the MPI SAMs were in the order of Pt < Pd < Ag < Au, reflecting the bonding nature between the -NC group and the substrate atoms.

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Section: Resultsmentioning

confidence: 99%

Substrate dependent structure of adsorbed aryl isocyanides studied by sum frequency generation (SFG) spectroscopy

Ito

Noguchi

Ikeda

et al. 2010

Phys. Chem. Chem. Phys.

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“…The angles between the planes defined by Fe(1)O(7)S and Fe(2)O(7)S is 85.5 °, which compares with 75.8° in hexacarbonyl-g-hydroxo-g-ditolylphosphido-diiron (II), Fe 2[P(p-C6H4CH3) 2]OH(CO)6 (Treichel et al, 1973), and 93.2 ° in o-aminothiophenolhexacarbonyldiiron (III), Fe2(C6HaSNH)(CO)6 (Le Borgne & Grandjean, 1973). The displacement of each Fe atom from the respective plane fit to the basal atoms of the tetragonal pyramid, O(7)SC(2)C(3) and O(7)SC(5)C(6), is 0.36 A; typical values range from 0.34 to 0.38 A (Treichel et aL, 1973). (I) displays an Fe-Fe bond similar in length to that in (III), 2.415 and 2.411 ,/k, respectively.…”

Section: (7jc(8)c(71smentioning

confidence: 92%

“…The coordination geometry of the formally Fe z atoms is similar to that observed previously. Description of that geometry is frequently presented in terms of two base-edge-shared [the O(7)...S edge] tetragonal pyramids (Treichel, Dean & Calabrese, 1973, and references therein). The following description conforms to that model.…”

Section: (7jc(8)c(71smentioning

confidence: 99%

The crystal and molecular structure of hexacarbonyl-[μ-(2,4-dimethyl-4-sulfido-2-penten-3-olato)-μ-O,μ-S]-diiron(Fe–Fe)

Jogun¹,

Stezowski²

1979

Acta Crystallogr Sect B

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A crystal structure analysis has been carried out for the title compound with data from a crystal cooled to ca The bonding geometry displays trans effects in the Fe-C carbonyl bonds opposite both coordinated atoms of the unique ligand. The effect is much greater trans to the Fe-O bond than trans to the Fe-S bond. The bond distances in the unique ligand are consistent with a nearly pure enolate structure.

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“…-2(4) C30 37( 4) 40 (3) 44 (3) 1 (3) -1 (3) -3(3) C31 39 (4) 38 (3) 71 ( 4 78 ( 4) 67 (3) 59 (3) -3(3) -25 (3) 0(2) 0(3) 77 (3) 37 (2) 46 (2) 2( 2) 11 (2)…”

Section: Determination Of the Absolute Configurationunclassified

Absolute configuration of organometallic compounds. 4. X-ray determination of the structure and absolute configuration of (-)579-(.eta.5-C5H5)Fe(CO)[P(C6H5)3]COOC10H19

Reisner¹,

Bernal²,

Brunner³

et al. 1978

Inorg. Chem.

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The structure and the absolute configuration of (-)s79-(75-C5H5)Fe(CO)[P(C6H5)3]COOC10H19 (C10H19 = menthyl) have been determined by single-crystal x-ray diffraction methods using data acquired by a computer-controlled diffractometer and Bijvoet's technique. The substance crystallizes in the orthorhombic system, space group P2,2121, with cell constants of a = 11.221 (4), b = 14.817 (7), and c = 18.958 (3) Á. The observed and calculated densities are 1.25 (2) and 1.25 g/cm3 (for Z = 4 molecules/unit cell). The Fe-(i)5-C5H5) fragment has normal distances and angles and the Cp ring is planar, as expected. The Fe-P(C6H|)3 group has stereochemical parameters which are well within the values found in the literature (i.e., Fe-P = 2.214 (2) A, P-C = 1.830 (6), 1.838 (4), and 1.853 (6) Á), and the dihedral angles of the three phenyl rings are canted at arbitrary values dictated by packing. The most important features of the stereochemistry of the molecule are the following: (1) the Fe-C(C=0) and C=0 distances are, respectively, 1.670 (7) and 1.206 (9) Á. . The former is the shortest iron to carbonyl carbon distance observed thus far. (2) The Fe-ester fragment shows a large angular distortion at the C atom such that Fe-C=0 = 132.1 (5), Fe-C-OC10Hi9 = 117.7 (4), and 0=C-O = 108.8(5)°. Concomitant with this distortion is a shortening of the Fe-C(ester) bond to 1.825 (6) Á. Both of these observations point to an enhanced r-bonding interaction between the iron atom and the carbons of the carbonyl and ester group. When the current rules for ranking groups are applied, the configuration at the iron atom is specified to be 5.

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Crystal and molecular structure of .mu.-hydroxo-.mu.-di(p-tolyl)phosphido-hexacarbonyldiiron, Fe2(CO)6[P(p-C6H4CH3)2]OH

Abstract: CO substitution reactions of metal carbonyls containing chelating phosphines (e.g., diphos) will depend on both steric and electronic effects.

Cited by 33 publications

References 15 publications

Substrate dependent structure of adsorbed aryl isocyanides studied by sum frequency generation (SFG) spectroscopy

Substrate dependent structure of adsorbed aryl isocyanides studied by sum frequency generation (SFG) spectroscopy

The crystal and molecular structure of hexacarbonyl-[μ-(2,4-dimethyl-4-sulfido-2-penten-3-olato)-μ-O,μ-S]-diiron(Fe–Fe)

Absolute configuration of organometallic compounds. 4. X-ray determination of the structure and absolute configuration of (-)579-(.eta.5-C5H5)Fe(CO)[P(C6H5)3]COOC10H19

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