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Dicyclopentamethylenethiuram Disulfide as Precursor of Mononuclear Complexes: Oxidative Cleavage of Metal-Metal Bond in [CpMo(CO)3]2 and Molecular Structure of cis-[CpMo(CO)2{S2C-N(CH2)5}]

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DOI: 10.4236/csta.2017.64006    449 Downloads   803 Views   Citations

ABSTRACT

The reaction of [CpMo(CO)3]2 with dicyclopentamethylenethiuram disulfide in refluxing xylene resulted a novel mono nuclear complex,
cis-[(CpMo(CO)2{S2C-N(CH2)5}] as red crystals in moderate yield. The compound was formed by the oxidative cleavage of metal-metal bond in [CpMo(CO)3]2 together with a reductive sulfur-sulfur bond scission in the ligand.

1. Introduction

Dithiocarbamate ligands are versatile ligands with applications in industry [1] , agriculture [2] and biology [3] . Since these ligands contain nitrogen and sulfur donor atoms, they are capable of forming complexes with most of the elements [4] . A number of dithiocarbamate complexes have been reported in literature [5] - [12] with various geometries such as square planar [13] , octahedral [14] [15] and trigonal prismatic [16] . Interestingly, their pyridine [6] [7] [17] , 2,2'-bipyridine [7] [9] triphenylphosphine [18] , and 1,10-phenanthroline [9] [17] adducts have been reported to possess similar donor properties. These ligands may stabilize monatomic metal ions in various oxidation states because of its chelating capacity thus forming mononuclear complexes [19] - [28] . The anionic form of N,N-dialkyl-1, 1-dithio-ligands is stable and the stability stems from the resonance of the anionic form of the ligand (Figure 1) [19] .

Shi et al. reported the reaction between [CpMo(CO)2]2 with tetramethylthiuram disulfide which yielded the mononuclear cyclopentadienyl molybdenum dithiocarbamate complex cis-[(CpMo(CO)2{S2C-N(CH3)2}] [29] . The compound is formed by oxidative cleavage of Mo-Mo triple bond together with a reductive S-S bond scission in tetramethylthiuram disulfide ligand (Scheme 1).

2. Results

We carried out the analogous reaction of dicyclopentamethylenethiuram disulfide with [CpMo(CO)3]2 and reported herein the formation of a mononuclear cyclopentadienyl molybdenum dicarbonyl complex, cis-[(CpMo(CO)2{S2C-N(CH2)5}].

Treatment of [CpMo(CO)3]2 with dicyclopentamethylenethiuram disulfide in refluxing xylene gave thermally stable complex cis-[(CpMo(CO)2{S2C-N(CH2)5}] as major reaction product (Scheme 2) which has been characterized by elemental analysis and spectroscopic methods [30] . The structure of the complex has been determined by single crystal X-ray diffraction [31] which is summarized in Figure 2.

Figure 1. Resonance structures of anioic N,N-dialkyl-1,1-dithio ligand.

Figure 2. Molecular structure of cis-[(CpMo(CO)2{S2C-N(CH2)5}].

Scheme 1. Oxidative cleavage of Mo-Mo triple bond in thiuram disulfide by [CpMo(CO)2]2.

Scheme 2. Synthesis of cis-[(CpMo(CO)2{S2C-N(CH2)5}].

The molecular structure of cis-[(CpMo(CO)2{S2C-N(CH2)5}] shows a four-legged piano-stool configuration at Mo(II), being coordinated to a bidentate cyclo pentamethylene dithiocarbamate and two CO ligands, similar to the coordination found in the analogous complex ion cis-[(CpMo(CO)2{S2C-N(CH3)2}] (Scheme 2) [29] . Bond lengths S(1)-C(3) and S(2)-C(3) have been found 1.708(5) Å, which is consistent with the partial C-S double bond [32] . The average Mo-C(Cp) bond distance in cis-[(CpMo(CO)2{S2C-N(CH2)5}] has been found to be 2.326 Å, which is similar to the Mo-C(Cp) average bond distance of 2.325 Å as found in cis-[(CpMo(CO)2{S2C-N(CH3)2}] [29] . Mo-S bond distance in cis-[(CpMo(CO)2{S2C-N(CH2)5}] was found 2.500 Å which is similar to the average Mo-S bond distance reported in cis-[(CpMo(CO)2{S2C-N(CH3)2}] (2.503 Å) [29] . Average Mo-CO bond distance in cis-[(CpMo(CO)2{S2C-N(CH2)5}] is 1.962 Å. Similar average Mo-CO bond distance 1.958 Å was found in cis-[(CpMo(CO)2{S2C-N(CH3)2}] (Figure 2) [29] .

Selected bond lengths [Å] and bond angles [˚]: Mo(1)-C(1) 1.958(6), Mo(1)-C(2) 1.966(6), Mo(1)-C(9) 2.275(6), Mo(1)-C(10) 2.300(6), Mo(1)-C(13) 2.306(6), Mo(1)-C(12) 2.363(6), Mo(1)-C(11) 2.384(6), Mo(1)-S(1) 2.505(2), Mo(1)-S(2) 2.495(3), S(1)-C(3) 1.708(5), S(2)-C(3) 1.708(5), C(2)-Mo(1)-C(1) 5.7(2), C(2)-Mo(1)-S(1) 81.47(19), C(1)-Mo(1)-S(1) 121.98(18), S(2)-Mo(1)-S(1) 68.55(7).

The complex, cis-[(CpMo(CO)2{S2C-N(CH2)5}] was obtained by the oxidative cleavage of the Mo-Mo bond in [CpMo(CO)3]2 which is consistent with the increase in oxidation number of Mo atom in the complex from +1 to +2. The geometry of the compound can be described as square-pyramidal with Cp-Mo defining the vertex and C(1), C(2), S(1) and S(2) atoms defining the base. The base of this complex is not a regular square because of unequal bond lengths of Mo-S and Mo-C bonds. In complex cis-[(CpMo(CO)2{S2C-N(CH2)5}], the cyclopentadienyl ligand acts as five electron donor and dithiocarbamate acts as three electron donor ligand. The complex is thermally stable and follows 18-electron rule.

Acknowledgements

The authors acknowledge ministry of science and technology, Bangladesh for financial assistance and Department of chemistry, Jahangirnagar University for providing the laboratory facility.

Supplementary Material

Crystallographic data for cis-[(CpMo(CO)2{S2C-N(CH2)5}] has been deposited at the Cambridge Crystallographic Centre with CCDC Reference Number CCDC 1567351. Copy of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/conts/retrieving.html (or from Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK (Tel: +441223 336408; fax: +44 1223 336033; email: deposit@ccdc.cam.ac.uk)).

Conflicts of Interest

The authors declare no conflicts of interest.

Cite this paper

Karim, M. , Islam, S. , RafikulIslam, M. , Karim, M. and Siddiquee, T. (2017) Dicyclopentamethylenethiuram Disulfide as Precursor of Mononuclear Complexes: Oxidative Cleavage of Metal-Metal Bond in [CpMo(CO)3]2 and Molecular Structure of cis-[CpMo(CO)2{S2C-N(CH2)5}]. Crystal Structure Theory and Applications, 6, 67-72. doi: 10.4236/csta.2017.64006.

References

[1] Amdio, E., Cavinato, G., Domella, A., Ronchini, L., Toniolo, L. and Vavasori, A. (2009) New Carboalkoxybis(Triphenylphosphine)Palladium(II) Cationic Complexes: Synthesis, Characterization, Reactivity and Role in the Catalytic Hydrocarboalkoxylation of Ethene. X-Ray Structure of Trans-[Pd(COOMe)(TsO)(PPh3)2]·2CHCl3. Journal of Molecular Catalysis A: Chemical, 298,103.
https://doi.org/10.1016/j.molcata.2008.10.002
[2] European Food Safety Authority (EFSA) (2011) The European Union Report on Pesticide Residues. EFSA, 9, 2430.
[3] Rehman, M., Hussain, A., Rehman, Z., Rauf, F.A., Hassan, A., Tahir, A. and Ali, S. (2010) New Tetrahedral, Square-Pyramidal, Trigonal-Bipyramidal and Octahedral Organotin(IV) 4-Ethoxycarbonylpiperazine-1-Carbodithioates: Synthesis, Structural Properties and Biological Applications. Journal of Organometallic Chemistry, 695, 1526.
https://doi.org/10.1016/j.jorganchem.2010.03.008
[4] Brown Jr., T.L., Lemayand, E.H. and Bursten, B.E. (2000) Chemistry: The Central Science. 8th Edition, Prentice Hall International, Washington.
[5] Doadrio, A.L., Sotelo, J. and Fern’andez-Ruano, A. (2002) Synthesis and Characterization of Oxovanadium(IV) Dithiocarbamates with Pyridine. Quimica Nova, 25, 525.
https://doi.org/10.1590/S0100-40422002000400002
[6] Sharma, M. and Sachar, R. (2009) Synthesis and Characterization of the Adducts of bis(N,N-Diethyldithiocarbamato)Oxovanadium(IV) with Substituted Pyridines. Oriental Journal of Chemistry, 25, 215.
[7] Manohar, A., Ramalingam, K., Bocelli, G. and Cantoni, A. (2010) Synthesis, Spectral and Single Crystal X-Ray Structural Studies on bis(2,2'-bipyridine)Sulphidom(II) (M = Cu or Zn) and Diaqua 2,2'-Bipyridine Zinc(II)Sulphatedihydrate. Journal of the Serbian Chemical Society, 75, 1085.
https://doi.org/10.2298/JSC091019097M
[8] Ekennia, A.C. (2013) Antibacterial Application of Novel Mixed-Ligand Dithiocarbamate Complexes of Nickel (II). Journal of Applied Chemistry, 5, 36.
[9] Geetha, N. and Thirumaran, S. (2008) Characterization Studies and Cyclic Voltammetry on Nickel(II) Amino Acid Dithiocarbamates with Triphenylphosphine in the Coordination Sphere. Journal of the Serbian Chemical Society, 73, 169.
https://doi.org/10.2298/JSC0802169G
[10] Sovilj, S.P., Vuckovic, G., Leovac, M. and Minic, D. (2000) Dinuclear Copper(II) Complexes of N,N',N",N"'-tetrakis(2-pyridylmethyl)-1,4,8,11-tetraazacyclotetradecane and Some N,S or N,O Bidentate Ligands. Polish Journal of Chemistry, 74, 945.
[11] Sharma, M., Sharma, A. and Sachar, R. (2013) Preparation and Characterization of the Adducts of bis(N,N-diethyldithiocarbamato)oxovanadium(IV) and copper(II) with n-propylamine and Isopropylamine. Chemical Science Transactions, 2, 367.
https://doi.org/10.7598/cst2013.265
[12] Sharma, M., Sharma, A. and Sachar, R. (2012) Synthesis and Characterization of the Adducts of Morpholinedithioccarbamate Complexes of Oxovanadium(IV), Nickel(II) and Copper(II) with Piperidine and Morpholine. Journal of Chemistry, 9, 1929.
https://doi.org/10.1155/2012/689501
[13] Onwudiwe, D.C. and Ajibade, P.A. (2011) Synthesis, Characterization and Thermal Studies of Zn(II), Cd(II) and Hg(II) Complexes of N-methyl-N-phenyl Dithiocarbamate: The Single Crystal Structure of [(C(6)H(5))(CH(3))NCS(2)](4)Hg(2). International Journal of Molecular Sciences, 12, 1964.
https://doi.org/10.3390/ijms12031964
[14] Osowole, A.A., Kolawole, G.A. and Fagade, O.E. (2005) Synthesis, Physicochemical, and Biological Properties of Nickel(II), Copper(II), and Zinc(II) Complexes of an Unsymmetrical Tetradentate Schiff Base and Their Adducts. Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry, 35, 829.
https://doi.org/10.1080/15533170500358168
[15] Kolawole, G.A. and Osowole, A.A. (2009) Synthesis and Characterization of Some metal(II) Complexes of Isomeric Unsymmetrical Schiff Bases and Their Adducts with Triphenylphosphine. Journal of Coordination Chemistry, 62, 1437.
https://doi.org/10.1080/00958970802621512
[16] Guo, T., Lai, C.S., Tan, X.J., Teo, C.S. and Tiekink, E.R. (2002) Bis(diethyldithiocarbamato) (4,7-dimethyl-1,10-phenanthroline)cadmium(II) Acetonitrile Solvate. Acta Crystallographica-Section E: Structure Reports Online, 58, 439.
https://doi.org/10.1107/S1600536802012679
[17] Shashi, B.K., Geetanjli, K. and Priyanka (2011) Synthesis and Characterization of Pyridine Adducts of Some Transition Metal 4-Methylpiperazine-1-Carbodithioic Acid Complexes. Himachal Pradesh University Journal, 1.
[18] Mamba, S.M. (2011) Synthesis, Characterization and Application of Dithiocarbamate Transition Metal Complexes. PhD Thesis, University of Johannesburg, Johannesburg.
[19] Karlin, K.D. (2005) Progress in Inorganic Chemistry. John Wiley and Sons, Inc., 53, 71.
[20] Deeming, A.J., Forth, C. and Hogarth, G. (2007) Synthesis and Crystal Structure of [Ru8(μ5-S)2(μ4-S)(μ3-S)(μ-CNMe2)2(μ-CO)(CO)15] Formed via the Double Sulphur-Carbon Bond Cleavage of dithiocarbamate ligands. Journal of Organometallic Chemistry, 692, 4000.
https://doi.org/10.1016/j.jorganchem.2007.05.044
[21] Karim, M.M., Abser, M.N., Hassan, M.R., Ghosh, N., Alt, H.G., Richards, I. and Hogarth, G. (2012) Oxidative-Addition of Thiuram Disulfides to Osmium(0): Synthesis of cis-[Os(CO)2(S2CNR2)2] (R = Me, Et, Cy, CH2CH2OMe) and Molecular Structures of cis-[Os(CO)2(S2CNMe2)2] and [(MeOCH2CH2)2NCS]2. Polyhedron, 42, 84.
https://doi.org/10.1016/j.poly.2012.04.042
[22] Ziegler, M.L., Weber, H., Nuber, B. and Serhadle, O. (1987) Synthesis and Characterization of the Zwitterion S2CC(NMe2)2, a Transition Metal Induced Carbon-Carbon Coupling. Complex Chemistry of the Zwitterions S2CC(NR2)2. Zeitschrift für Naturforschung, 42b, 141.
[23] Catheline, D., Roman, E. and Astruc, D. (1984) Reactivity of the Monodentdithiocarbamate Ligand in CpFe(CO)2(η1-S2CNR2). Inorganic Chemistry, 23, 4508.
https://doi.org/10.1021/ic00194a021
[24] Maheu, L.J., Miessler, G.L., Berry, J., Burow, M. and Pignolet, L.H. (1983) Di- and Tri-thiocarbamato Complexes of Osmium(III) and the Crystal and Molecular Structure of [Os2(SeS2CNMe2)2(S2CNMe2)3]PF6. Inorganic Chemistry, 22, 405.
https://doi.org/10.1021/ic00145a009
[25] Hope, J.M., Martin, R.L., Taylor, D. and White, A.H. (1977) Ring Expansion in a Metal-Dithiocarbamate Complex by Oxygen Insertion; Synthesis and Properties of [Cr(S2CNR2)2(OS2CNR2)]. The X-Ray Structure of bis[NN-diethyl (dithiocarbamato-SS’)][NN-diethyl(dithioperoxycarbamato-OS)]chromium(III). Journal of the Chemical Society, Chemical Communications, 99.
https://doi.org/10.1039/C39770000099
[26] Martin, R.L., Patrick, J.M., Skelton, B.W., Taylor, D. and White, A.H. (1982) Crystal Structure of bis[N,N-diethyl(dithiocarbamato-S,S’)]-[N,N-diethyl(dithioperoxycarbamato-O,S)]chromium(III). A Redetermination. Australian Journal of Chemistry, 35, 2551.
https://doi.org/10.1071/CH9822551
[27] Fackler, J.P. and Holah, D.G. (1966) Sulfur Chelates. II. Five-Coordinate Transition Metal Complexes. Inorganic and Nuclear Chemistry Letters, 2, 251.
https://doi.org/10.1016/0020-1650(66)80055-7
[28] Pignolet, L.H., Lewis, R.A. and Holm, R.H. (1971) Synthesis and Stereochemical Rearrangements of Complexes Containing the Fe-S6 Core. Journal of the American Chemical Society, 93, 360.
https://doi.org/10.1021/ja00731a011
[29] Shi, Y., Cheng, G., Lu, S., Guo, H., Wu, Q., Huang, X. and Hu, N. (1993) The Cleavage Reaction of the Molybdenum-Molybdenum Triple Bond. The Crystal Structures of Molybdenum Complexes [CpMo(CO)2(C5H4NS)], [CpMo(CO)2 (C9H6NS)]O:PPh3 and [CpMo(CO)2(S2CNMe2)]. Journal of Organometallic Chemistry, 455, 115.
https://doi.org/10.1016/0022-328X(93)80389-S
[30] To a xylene (40 mL) of [CpMo(CO)3]2 (0.200 g, 0.408 mmol) Was Added Dicyclopentamethylenethiuram Disulfide (0.196 g, 0.612mmol) and the Reaction Mixture Was Refluxed for 1 Hour. The Color Was Changed from Red to Red Brown. The Solvent Was Removed under Reduced Pressure and Residue Chromatographed by TLC on Silica. Elution with Cyclohexane/Dichloromethane (3:2 V/V) Gave One Band cis-[(CpMo(CO)2{S2C-N(CH2)5}] (0.167 g, 36.16%) as Red Brown Crystal from Dichloromethane/Hexane Mixture at ?4 oC. Elemental Analysis: Found C = 41.36, H = 3.99, N = 3.70, S = 16.94% and C13H15MoNO2S2 Requires C = 41.34, H = 3.98, N = 3.71, S = 16.96%. IR (υCO) in cm?1: 1857.53(s), 1949.15(s). 1H NMR (ppm): 1.54 (m, 3H), 1.63 (m, 3H), 3.56 (m, 2H), 3.79 (m, 2H), 5.41 (s, 5H). FAB mass (m/z):377 [M+], 349 [M+-CO], 321 [M+-2CO], 257 [M+-2CO-2S], etc.
[31] Crystal Data for cis-[(CpMo(CO)2{S2C-N(CH2)5}]: Empirical Formula C13H15MoNO2S2, MW = 377.32, Triclinic, Space groupP1, a = 6.449(7) A, b = 10.634(10) A, c = 11.383(12) A, α = 71.94(3)°, β = 82.31(3)°,γ = 76.43(3)°, V =719.9(13) A3, T= 273(2) K, Z= 2, μ=1.197 mm-1, F(000) 380, density (calculated) 1.741 Mg/m3, 7722 Reflections Collected, 3303 Independentreflections [R(int) = 0.0477]. The Final R1 = 0.0486, wR2 = 0.1288 [I > 2σ (I)], R Indices (all data) R1 = 0.0719, wR2 = 0.1566.
[32] Lide, D.R. (2003-2004) Handbook of Chemistry and Physics. 84th Edition, CRC Press, Sec. 9, 10.

  
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