NDLI: Hemilabile and reversible carbon monoxide binding properties of iron(II), cobalt(II) and nickel(II) complexes containing a new tridentate P–S

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Kealey, Steven Long, Nicholas J. Vilar, Ramon Gee, Antony D. Demello, Andrew Tate, Christopher W. White, Andrew J. P.
Description	Author Affiliation: Tate CW ( Department of Chemistry, Imperial College, London, UK SW7 2AZ.)
Abstract	Several first-row transition metal complexes of the formulation $[M(1)_{2}](X)_{2}$ {where 1 = $Ph_{2}PCH_{2}CH_{2}S(2-C_{6}H_{4}NH_{2});$ M = $Fe^{II},$ X = $BF_{4}^{−}$ (2); M = $Co^{II},$ X = $BF_{4}^{−}$ (3), $Ni^{II},$ X = $ClO_{4}^{−}$ (4)} have been prepared by reaction of two equivalents of the new P–S–N ligand $Ph_{2}PCH_{2}CH_{2}S(2-C_{6}H_{4}NH_{2})$ 1 with one equivalent of the appropriate $[M(OH_{2})_{6}](X)_{2}$ precursor in acetonitrile . In the solid state, complexes 2–4 exist as distorted centrosymmetric octahedral structures featuring facially capping ligands in an all-trans arrangement. Reaction of 2 and 3 with a stream of carbon monoxide (1 atm.) for 5 min in acetonitrile generates iron(II) monocarbonyl species of formulation $[Fe(CO)(1)_{2}](BF_{4})_{2}2a,$ and a cobalt(II) dicarbonyl complex, $[Co(CO)_{2}(1)_{2}](BF_{4})_{2}3a,$ which can be isolated in the solid state. Complete removal of CO is achieved by either heating to reflux samples of 2a in acetonitrile for 5 min or by heating solid samples of 3a at 120 °C in vacuo over a period of 4 h. The binding of carbon monoxide is fully reversible for 2 and 3 and can be repeated over multiple cycles. When the same trapping reactions were carried out with very low radiochemical $^{11}CO$ concentrations, metal carbonyl species were no longer formed. It is likely that the kinetics of $^{11}CO$ adduct formation are too slow to allow for effective trapping under the applied radiochemical conditions.
ISSN	14779226
Issue Number	1
Volume Number	41
e-ISSN	13645447
Journal	Dalton Trans.
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2012-01-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Carbon Monoxide Chemistry Cobalt Coordination Complexes Ferrous Compounds Nickel Carbon Radioisotopes Chemical Synthesis Crystallography, X-Ray Ligands Molecular Conformation Nitrogen Phosphorus Spectrophotometry, Infrared Sulfur Journal Article Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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