Iron tris(dimethyldithiocarbamate)

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Iron tris(dimethyldithiocarbamate)
Names
IUPAC name
Tris(dimethyldithiocarbamato)iron
Other names
Ferric dimethyl dithiocarbamate, Ferbam
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.034.970 Edit this at Wikidata
EC Number
  • 238-484-2
KEGG
RTECS number
  • NO8750000
UNII
UN number 3077, 2771
  • InChI=1S/3C3H7NS2.Fe/c3*1-4(2)3(5)6;/h3*1-2H3,(H,5,6);/q;;;+3/p-3
    Key: WHDGWKAJBYRJJL-UHFFFAOYSA-K
  • coordination form: CN(C)C(S1)S[Fe]123(SC(S2)N(C)C)SC(S3)N(C)C
  • ionic form: CN(C)C(=S)[S-].[Fe+3].CN(C)C(=S)[S-].CN(C)C(=S)[S-]
Properties
[(CH3)2NCS2]3Fe
Molar mass 416.5 g/mol
Appearance Dark brown to black, odorless solid[1]
Density 1.52 g/cm3
Melting point Decomposes above 180 °C (356 °F)[1]
Boiling point Decomposes[1]
0.01% (20 °C)[1]
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Reacts with strong oxidizers, moisture[1]
Lethal dose or concentration (LD, LC):
3000 mg/kg (rabbit, oral)
2000 mg/kg (guinea pig, oral)
1130 mg/kg (rat, oral)
3400 mg/kg (mouse, oral)[2]
NIOSH (US health exposure limits):
PEL (Permissible)
 TWA 15 mg/m3[1]
REL (Recommended)
 TWA 10 mg/m3[1]
IDLH (Immediate danger)
 800 mg/m3[1]
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).

Iron tris(dimethyldithiocarbamate) is the coordination complex of iron with dimethyldithiocarbamate with the formula Fe(S2CNMe2)3 (Me = methyl). It is marketed as a fungicide.[3]

Synthesis, structure, bonding[edit]

Iron tris(dithiocarbamate)s are typically are prepared by salt metathesis reactions.[3]

Iron tris(dimethyldithiocarbamate) is an octahedral coordination complex of iron(III) with D3 symmetry.[4]

Spin crossover (SCO) was first observed in 1931 by Cambi et al. who discovered anomalous magnetic behavior for the tris(N,N-dialkyldithiocarbamatoiron(III) complexes.[5] The spin states of these complexes are sensitive to the nature of the amine substituents.[6]

Reactions[edit]

Iron tris(dithiocarbamate)s react with nitric oxide to give a nitrosyl complex:

Fe(dtc)3 + NO → Fe(dtc)2NO + 0.5 (dtc)2

This efficient chemical trapping reaction provides a means to detect NO.[7]

Reflecting the strongly donating properties of dithiocarbamate ligands, iron tris(dithiocarbamate)s oxidize at relatively mild potentials to give isolable iron(IV) derivatives [Fe(S2CNR2)3]+.[8]

Iron tris(dithiocarbamate)s react with hydrochloric acid to give the pentacoordinate chloride:[9]

Fe(dtc)3 + HCl → Fe(dtc)2Cl + Hdtc

Safety[edit]

The U.S. Occupational Safety and Health Administration (OSHA) has set the legal (permissible exposure limit) for ferbam exposure in the workplace as 15 mg/m3 over an 8-hour workday. The U.S. National Institute for Occupational Safety and Health (NIOSH) has set a recommended exposure limit (REL) of 1 mg/m3 over an 8-hour workday. At levels of 800 mg/m3, ferbam is immediately dangerous to life and health.[1]

See also[edit]

References[edit]

  1. ^ a b c d e f g h i NIOSH Pocket Guide to Chemical Hazards. "#0286". National Institute for Occupational Safety and Health (NIOSH).
  2. ^ "Ferbam". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  3. ^ a b D. Coucouvanis (2007). "The Chemistry of the Dithioacid and 1,1-Dithiolate Complexes". Progress in Inorganic Chemistry. 11: 233–371. doi:10.1002/9780470166123.ch4. ISBN 978-0-470-16612-3.
  4. ^ J. Albertsson; Å. Oskarsson (1977). "Compounds with intermediate spin. I. The crystal structure of tris(N,N-dimethyldithiocarbamato)iron(III) at 150 and 295 K". Acta Crystallographica Section B. 33 (6): 1871–1877. doi:10.1107/s0567740877007237.
  5. ^ L. Cambi; L and L. Szego (1931). "Über die magnetische Susceptibilität der komplexen Verbindungen". Chem. Ber. Dtsch. Ges. 64 (10): 2591. doi:10.1002/cber.19310641002.
  6. ^ P. Gütlich; H.A. Goodwin (2004). Spin Crossover in Transition Metal Compounds I. Springer Berlin. ISBN 978-3-540-40396-8.
  7. ^ Fujii, S.; Yoshimura, T. (2000). "A New Trend in Iron–Dithiocarbamate Complexes: as an Endogenous NO Trapping Agent". Coordination Chemistry Reviews. 198: 89–99. doi:10.1016/S0010-8545(99)00196-4.
  8. ^ Pasek, E. A.; Straub, D. K. (1972). "Tris(N,N-Disubstituted Dithiocarbamato)iron(IV) Tetrafluoroborates". Inorganic Chemistry. 11 (2): 259–263. doi:10.1021/ic50108a012.
  9. ^ Martin, R. L.; White, A. H. (1967). "A Novel Series of fFive-Coordinated Iron(III) Complexes with the Square-Pyramidal Configuration and Spin, S = 3/2". Inorganic Chemistry. 6 (4): 712–717. doi:10.1021/ic50050a016.
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