(1'-Benzoylferrocenyl)diphenylmethanol; a Centrosymmetric R⁴₄(16) Dimer Generated by C-H...O Hydrogen Bonding

In (1'-benzoylferrocenyl)diphenylmethanol, [(PhCOC₅H₄)Fe(C₅H₄)]CPh₂OH, (C₃₀H₂₄FeO₂), there is an intramolecular O-H...O hydrogen bond with O...O 2.891 (2) Å: the ferrocenyl unit adopts an eclipsed conformation and the molecules are linked into centrosymmetric dimers by C-H...O hydrogen bonds with C...O 3.357 (3) Å, to generate a cyclic R⁴₄(16) motif

Accurate Redeterminations of 1,1'-Dibenzoylferrocene and (4-Nitrophenyl)ferrocene

In the solid state, molecules of 1,1'-dibenzoylferrocene, [Fe(C₁₂H₉O)₂], (I), are linked to form infinite chains in the [100] direction via (cyclopentadienyl)C-H...O hydrogen bonds [C...O 3.354 (4) Å]. In the structure of (4-nitrophenyl)ferrocene, [Fe(C₅H₅)(C₁₁H₈NO₂)], (II), there are no C-H...O hydrogen bonds and molecules are separated by normal van der Waals distances. For earlier determinations see Struchkov [Dokl. Akad. Nauk SSSR (1956), 110, 67-70] for (I) and Roberts et al. [J. Chem. Soc. Dalton Trans. (1988), pp. 1549-1556] for (II)

Oxidation of ferrocenyl ketones using selenium(IV) oxide:Crystal and molecular structures of racemic 2,3-diferrocenyl-1,4-diphenylbutane-1,4-dione, racemic and meso 2,3-diferrocenyl-1,4-bis(4-biphenylyl) butane-1,4-dione, and ferrocenylmethyl(4-biphenylyl) ketone

Oxidation of the ferrocenyl ketones FcCH2COR 1 [Fc = (C5H5)Fe(C5H4); a R = Ph, b R = C6H4Ph-4] with selenium(IV) oxide provides only modest yields of the corresponding 1,2-diketones FcCOCOR 2, but substantial yields of the 1,4-butanediones RCOCH(Fc)CH(Fc)COR 3 resulting from C-C coupling. Compounds 3 exist in two diastereoisomeric forms, racemic and meso, and crystal structures are reported for rac-3a, rac-3b and meso-3b, as well as for 1b.</p

Accurate Redeterminations of 1,1\u27-Dibenzoylferrocene and (4-Nitrophenyl)ferrocene

In the solid state, molecules of 1,1\u27-dibenzoylferrocene, [Fe(C₁₂H₉O)₂], (I), are linked to form infinite chains in the [100] direction via (cyclopentadienyl)C-H...O hydrogen bonds [C...O 3.354 (4) Å]. In the structure of (4-nitrophenyl)ferrocene, [Fe(C₅H₅)(C₁₁H₈NO₂)], (II), there are no C-H...O hydrogen bonds and molecules are separated by normal van der Waals distances. For earlier determinations see Struchkov [Dokl. Akad. Nauk SSSR (1956), 110, 67-70] for (I) and Roberts et al. [J. Chem. Soc. Dalton Trans. (1988), pp. 1549-1556] for (II)

Synthesis of ferrocenyl-1,2-diketones and related compounds:Crystal and molecular structures of 1,2-diferrocenylethanedione and 1-ferrocenyl-2-(4-biphenylyl) ethanedione

Ferrocenyl-1,2-diketones FcCOCOR, 3, [Fc = (C5H5)Fe(C5H4)] can be prepared by oxidation of acylferrocenes FcCOCH2R or, more efficiently, by oxidation of the isomeric ketones FcCH2COR, 2. The ketones 2 are in turn readily synthesized from the salt (FcCH2PPh3)+I- via the acylated salts [FcCH(COR)PPh3]+I-. The haloacylferocenes FcCOCClxH3-x (x = 1, 2, 3, of which the x = 2 example is synthetically equivalent to a diketone) are synthesized by Friedel-Crafts acylation of ferrocene using CClxH3-xCOCl/AlCl3, but the reaction proceeds via two parallel pathways, one giving the normal acyl derivatives FcCOCClxH3-x and the other giving the reduced products FcCOCClx-1H4-x. Two diketones FcCOCOFc 3b and FcCOCOC6H4Ph 3c have been structurally characterised by single-crystal X-ray diffraction.</p

Synthesis of ferrocenyl-1,2-diketones and related compounds:Crystal and molecular structures of 1,2-diferrocenylethanedione and 1-ferrocenyl-2-(4-biphenylyl) ethanedione

Ferrocenyl-1,2-diketones FcCOCOR, 3, [Fc = (C5H5)Fe(C5H4)] can be prepared by oxidation of acylferrocenes FcCOCH2R or, more efficiently, by oxidation of the isomeric ketones FcCH2COR, 2. The ketones 2 are in turn readily synthesized from the salt (FcCH2PPh3)+I- via the acylated salts [FcCH(COR)PPh3]+I-. The haloacylferocenes FcCOCClxH3-x (x = 1, 2, 3, of which the x = 2 example is synthetically equivalent to a diketone) are synthesized by Friedel-Crafts acylation of ferrocene using CClxH3-xCOCl/AlCl3, but the reaction proceeds via two parallel pathways, one giving the normal acyl derivatives FcCOCClxH3-x and the other giving the reduced products FcCOCClx-1H4-x. Two diketones FcCOCOFc 3b and FcCOCOC6H4Ph 3c have been structurally characterised by single-crystal X-ray diffraction.</p

Solid triphenylmethanol: a molecular material that undergoes multiple internal reorientational processes on different timescales

In solid triphenylmethanol, the molecules are arranged in hydrogen-bonded tetramers, and it is already well established that the hydrogen bonding in this material undergoes a dynamic switching process between different hydrogen bonding arrangements. In addition to this motion, we show here, from solid-state 2H NMR studies of the deuterated material (C6D5)3COH, that each phenyl ring in this material undergoes a 180°-jump reorientation about the C6D5–C(OH) bond, with an activation energy of ca. 50 kJ mol−1. The timescale for the phenyl ring dynamics is several orders of magnitude longer than the timescale for the hydrogen bond dynamics in this material, and is uncorrelated with the dynamics of the hydrogen bonding arrangement