12129-67-8Relevant articles and documents
ARENE EXCHANGE REACTIONS OF (ARENE)TRICARBONYLCHROMIUM COMPLEXES.
Traylor,Stewart,Goldberg
, p. 4445 - 4454 (1984)
The kinetics of the reaction of (arene)tricarbonylchromium complexes with arenes have been investigated. The uncatalyzed reaction is first order in complex and first order in arene, indicating a displacement process. The reaction is catalyzed by cyclohexanone in a process which is first order in cyclohexanone and independent of arene concentration. The unreactive (hexamethylbenzene)tricarbonylchromium catalyzes exchange between benzene and (p-xylene)tricarbonylchromium, verifying and clarifying the results of Strohmeier. A simplified mechanism is proposed which incorporates the first-order, the second-order, and the catalyzed processes without requiring the production of free tricarbonylchromium.
Photochemical synthesis of new (η6-arene)Cr-hydrido stannyl and (η6-arene)Cr-bis-stannyl complexes. Ligand effects on the Sn-H interaction in the hydrido stannyl compounds
Khaleel, Abbas,Klabunde, Kenneth J.,Johnson, Alison
, p. 11 - 20 (2007/10/03)
Hydrido stannyl compounds containing the η2-H-SnPh3 ligand and bis-stannyl compounds containing two SnPh3 ligands have been obtained from the photolysis of (η6-arene)Cr(CO)3 and HSnPh3. New complexes with different arenes (mesitylene, trifluorotoluene and 1,4-dimethoxybenzene) have been obtained and characterized by X-ray diffraction: (η6-C6H4(OCH3) 2)Cr(CO)2(HSnPh3) (3a), (η6-C6H4(OCH3) 2)Cr(CO)2(SnPh3)2 (3b). Structural data for 3a: monoclinic; space group P21/c (No. 14); a=17.445(3), b=9.820(3) and c=16.302(5) A; Z=4; V=2539.2(12) A3; 3b: monoclinic; space group P21/n (No. 14); a=13.904(3), b=20.567(5) and c=13.911(3) A; Z=4; V=3994(2) A3. 1H-NMR as well as X-ray provided evidence for the existence of three-center two-electron bonds in the hydrido stannyl complexes. The effects of different ligands on bonding and spectroscopic parameters were studied. Arene exchange reactions of the bis-stannyl complexes, as well as reactions of some of these compounds with P(C2H5)3 and CO, were also investigated.
Laser pulse photolysis and transient infrared investigation into the effect of solvent or substituents (X) on the reactivity of photogenerated (η6-C6H6-yXy)Cr(CO)2 intermediates
Creaven, Bernadette S.,George, Michael W.,Ginzburg, Allan G.,Hughes, Catherine,Kelly, John M.,Long, Conor,McGrath, Irene M.,Pryce, Mary T.
, p. 3127 - 3131 (2008/10/08)
Time-resolved infrared spectroscopy identified the first observable species following nanosecond laser photolysis of (benzene)Cr(CO)3 in alkane solution as (benzene)Cr(CO)2(alkane). UV/ vis-monitored laser flash photolysis was used to observe the reaction of this species with CO. The reactivity toward CO of the primary photoproducts derived from related arene complexes (arene = C6H5Cl, C5H5Me, p-ClC6H4Me, C6H5Et, C6H5But, o- and p-C6H4Me2, C6H3Me3, C6Me6, C6Et6) were also determined by this technique. The rate of reaction with CO was found to depend on the alkane solvent and on the nature and degree of substitution of the arene ligand. The enthalpies of activation for all reactions were constant (24 ± 2 kJ mol-1), while the entropy of activation increased upon methyl substitution of the arene and upon a change in the solvent from cyclohexane to a linear alkane.
