Products and Kinetics of the Reaction of Monomeric Target Bis-(Acetylacetonato) Copper(II) with Transmetalator Bis-(Diethoxydithiophosphato) Zinc(II) in Methylene Chloride

Hisham A. Abo-Eldahab^1,2

¹Chemistry Department, Faculty of Science, Alexandria, Egypt.
²Umm Al-Qura University, University College, Makkah, KSA.

DOI: 10.4236/ojpc.2015.52005                

Abstract

Reaction of bis-(acetylacetonato) copper(ΙΙ) (A) with transmetalator Zn((EtO)₂PS₂)₂ (B₂; Et = ethyl) in methylene chloride is a simple irreversible second-order process over a wide temperature range which is the first example of a second-order reaction of mononuclear target A with a transmetalator. The plots of k_obsd vs [A] are linear, meaning that there is one A and one B₂ in the activated complex of the slowest reaction step. The slowest step is precursor formation on the basis that B₂ is an exceptionally weak complex. The product of the A/B₂ reaction is the strong successor complex Zn(acac)₂•Cu(ps)₂. The data are compared with those for reactions of the same target (A) with S-methyle isopropylidenehydrazinecarbodithioate-carbodithioato-metal(II) complexes M(SN)₂ (M=Ni (C₁) and Zn (C₂)). The reaction is not like that of A with Ni ((MeO)₂PS₂)₂ (B₁; Me=methyl), because it is irreversible and also consistent with the measured lower relative thermodynamic stability of B₂ compared to B₁.

Keywords

Kinetics, Mechanism, Transmetalation, Transmetallators, Thermodynamics

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1]	El-Toukhy, A., Cal, G.Z., Davies, G., Gilbert, T.R., Onan, K.D. and Veidis, M. (1984) Transmetalation Reactions of Tetranuclear Copper(II) Complexes. 2. Stoichiometry and Products of Reaction of [(DENC)CuCl]4O2, [(DENC)CuCl]4(CO3)2, [(DENC)CuCl]4Cl4, and (DENC)4Cu4Cl6O (DENC = N,N-Diethylnicotinamide) with Ni(NS)2, the Kinetics of Product Isomerization in Aprotic Solvents, and Inhibition of Copper-Catalyzed Phenolic Oxidative Coupling by Dioxygen through Transmetalation. Journal of the American Chemical Society, 106, 4596-4605. http://dx.doi.org/10.1021/ja00328a050
[2]	Davies, G., El-Sayed, M.A. and El-Toukhy, A. (1989) Transmetalation: A New Route to Heteropolymetallic Molecules and Materials. Comments on Inorganic Chemistry, 8, 203-220. http://dx.doi.org/10.1080/02603598908035795
[3]	Cai, G.Z., Davies, G., El-Sayed, M.A., El-Toukhy, A., Gilbert, T.R., Karlin, K.D. and Zubieta, J., Eds. (1986) Biological and Inorganic Copper Chemistry, Vol. 2. Adenne, Guilderland, 237.
[4]	Davies, G., El-Sayed, M.A., El-Toukhy, A., Gilbert, T.R. and Nabih, K. (1986) Transmetalation of Tetranuclear Copper Complexes. 5. Transmetalation of Copper(I) Complexes and Stoichiometry and Kinetics of Oxidation of Neutral Tetranuclear (DENC)3Cu3M(NS)X4 (DENC = N,N-Diethylnicotinamide) Complexes by Dioxygen in Aprotic Solvents. Inorganic Chemistry, 25, 1929-1934. http://dx.doi.org/10.1021/ic00232a004
[5]	Davies, G., El-Kady, N., El-Sayed, M.A., El-Toukhy, A. and Schure, M.R. (1988) The Kinetics of Primary Events in the Reaction of L2Cu2X2 Complexes (L is an N,N,N'N'-Tetraalkyldiamine, X is Cl or Br) with M(NS)2 Reagents. Inorganica Chimica Acta, 149, 31-43. http://dx.doi.org/10.1016/S0020-1693(00)90565-6
[6]	Davies, G., El-Sayed, M.A., El-Toukhy, A., Henary, M. and Gilbert, T.R. (1986) Transmetalation of Tetranuclear Copper Complexes. 8. Transmetalation of Tetranuclear Copper(I) Complexes with a Co(NS)3 Reagent. Inorganic Chemistry, 25, 2373-2377. http://dx.doi.org/10.1021/ic00234a019
[7]	Davies, G., El-Sayed, M.A. and El-Toukhy, A. (1986) Transmetalation of Tetranuclear Copper Complexes. 7. Spectral Evidence for the Substoichiometric Transmetalation of (.mu.4-O)[(DENC)Cu]4X6 Complexes (DENC = N,N-Diethyl-nicotinamide; X = Cl or Br) by a Bis(Acetone S-Methyl Hydrazonecarbodithioato)Nickel Reagent. Inorganic Chemistry, 25, 2269-2271. http://dx.doi.org/10.1021/ic00233a036
[8]	Henary, M., Davies, G., Abu-Raqabah, A., EI-Sayed, M.A. and El-Toukhy, A. (1988) Progressive Transmetalation of Tetranucleardioxocopper (II) Complexes with Cobalt Reagents. Inorganic Chemistry, 27, 1872.
[9]	Davies, G., El-Sayed, M.A., El-Toukhy, A., Henary, M. and Martin, C.A. (1986) Distinguishable Sites in Tetranuclear Oxocopper(II) Complexes (py)3Cu4Cl4O2 and (DENC)3Cu3M(H2O)Cl4O2 (M = Co, Ni, Cu, Zn). Inorganic Chemistry, 25, 4479-4487. http://dx.doi.org/10.1021/ic00245a007
[10]	Davies, G., El-Sayed, M.A., El-Toukhy, A., Henary, M., Kassem, T.S. and Martin, C.A. (1986) Selective Transmetalation and Demetalation of Heteropolynuclear Metal Complexes. Inorganic Chemistry, 25, 3904-3909. http://dx.doi.org/10.1021/ic00245a007
[11]	Davies, G., El-Sayed, M.A. and El-Toukhy, A. (1986) Transmetalation of Tetranuclear Copper Complexes. 4. Structural Implications of the Kinetics of Direct Transmetalation of Tetranuclear Copper(II) Complexes by Ni(NS)2 Reagents. Inorganic Chemistry, 25, 1925-1928. http://dx.doi.org/10.1021/ic00232a003
[12]	Davies, G., El-Sayed, M.A. and El-Toukhy, A. (1986) Transmetalation of Tetranuclear Copper Complexes. 9. Stoichiometry and Kinetics of Transmetalation of (μ4-O)[NCu]4X6 Complexes by M(NS)2 Reagents in Aprotic Solvents. Inorganic Chemistry, 25, 3899-3903. http://dx.doi.org/10.1021/ic00242a015
[13]	Abu-Raqabah, A., Davies, G., El-Sayed, M.A., El-Toukhy, A. and Henary, M. (1989) Limits of Direct Transmetalation of Polynuclear Copper(II) Complexes with M(NS)n Reagents. Scissor Transmetalators. Synthesis and Properties of the Trimers (μ3-O)(N,py)3Cu3X4 (N = N,N-Diethylnicotinamide; py = Pyridine; X = Cl, Br). Inorganic Chemistry, 28, 1156-1166. http://dx.doi.org/10.1021/ic00305a027
[14]	El-Sayed, M.A., El-Wakil, H., Ismail, K.Z., El-Zayat, T.A. and Davies, G. (1998) Stiochiometry, Product and Kinetics of Catalytic Oxidation of 2,6-Dimethylphenol by Bromo(N,N'-Diethylenediamine)Copper Complexes in Methylene Chloride. Transition Metal Chemistry, 23, 795-800. http://dx.doi.org/10.1023/A:1006970209841
[15]	Davies, G., El-Sayed, M.A., El-Toukhy, A. and Henary, M. (1990) Transmetalation of Tetranuclear Copper (I) Complexes with an Fe(NS)3 Reagent. Inorganica Chimica Acta, 168, 65-76.
[16]	Davies, G., El-Toukhy, A., Veidis, M. and Onan, K.D. (1984) Transmetalation Reactions of Tetranuclear Copper(II) Complexes. I. Crystal and Molecular Structures of an Intermediate and a Final Product of Reaction of Di-μ-oxo-tetra [chloro(DENC)copper(II)], (DENC = N,N-Diethylnicotinamide) with [Zn(N2S2)], (N2S2 = Diacetylbis(hydrazonato-S-methylcarbodithioate) in Aprotic Solvents. Inorganica Chimica Acta, 84, 41-50.
[17]	El-Sayed, M.A., Abu-Raqabah, A., Davies, G. and El-Toukhy, A. (1989) Kinetic Proof That the Tetranuclear Oxocopper(II) Complex (py)3Cu4Cl4O2 Initiates and Catalyzes the Oxidative Coupling of 2,6-Dimethylphenol by Dioxygen in Nitrobenzene. Inorganic Chemistry, 28, 1909-1914. http://dx.doi.org/10.1021/ic00309a028
[18]	Mazik, J.V., Carriera, L.G. and Davies, G. (1988) Cu-Ni Alloy Formation by Reduction in Hydrogen of a Polyheterometallic Complex. Journal of Materials Science Letters, 7, 833-835. http://dx.doi.org/10.1007/BF00723777
[19]	Davies, G., Giessen, B.C. and Shao, H.L. (1990) Single-Phase Cu0.50Ni0.50 Alloy Preparation by Thermolysis of a Simple Heteropolymetallic Precursor. Materials Letters, 9, 231-234. http://dx.doi.org/10.1016/0167-577X(90)90051-M
[20]	Al-Shehri, S., Davies, G., El-Sayed, M.A. and El-Toukhy, A. (1990) Rate Law Variations in the Specific Monotransmetalation of (μ4-O)(N,py)4Cu4−x MxX6 Complexes with Zn(NS)2 in Nitrobenzene. Inorganic Chemistry, 29, 1206-1210.
[21]	El-Sayed, M.A. and Davies, G. (1990) Stoichiometry, Products and Kinetics of Monotransmetalation and Complexation of Dimeric Complexes [N2CuCl2]2 and [N2NiCl2]2 (N Is N,N-Diethylnicotinamide) with M(NS)2 Reagents in Nitrobenzene. Inorganica Chimica Acta, 173, 163-173. http://dx.doi.org/10.1016/S0020-1693(00)80209-1
[22]	Ali, A. and Davies, G. (1990) Products and Kinetics of the Reactions of Bis-(acetylacetonato)copper(II) with Ni(NS)2 and Cu(NS)2 Reagents in Methylene Chloride. Inorganica Chimica Acta, 177, 167-178. http://dx.doi.org/10.1016/S0020-1693(00)85973-3
[23]	Ali, A. and Davies, G. (1991) Cooperativity in Metal Exchange Reactions of Bis(acetylacetonato)copper(II) with Co(NS)2 and Zn(NS)2 Reagents in Methylene Chloride. Inorganica Chimica Acta, 179, 245-254. http://dx.doi.org/10.1016/S0020-1693(00)85884-3
[24]	Zhang, C.X., Kaderli, S., Costas, M., Kim, E., Neuhold, Y.M., Karlin, K.D. and Zuberbuhler, A.D. (2003) Copper(I)-Dioxygen Reactivity of [(L)CuI]+ (L = Tris(2-pyridylmethyl)amine): Kinetic/Thermodynamic and Spectroscopic Studies Concerning the Formation of Cu-O2 and Cu2-O2 Adducts as a Function of Solvent Medium and 4-Pyridyl Ligand Substituent Variations. Inorganic Chemistry, 42, 1807-1824. http://dx.doi.org/10.1021/ic0205684
[25]	Kastalsky, V. and MaConnel, J.F. (1969) The Crystal and Molecular Structure of Bis(dimethyldithiophosphato)nickel(II), Ni[(CH3O)2PS2]2. Acta Crystallographica Section B, 25, 909-915. http://dx.doi.org/10.1107/S0567740869003207
[26]	El-Sayed, M.A., Abdel-Hamid, I.A., El-Zayat, T.A. and Abdel-Salam, A.H. (2006) Oxidation of Bis(μ-halo)-Bis[(diamine)copper(I)] Complexes [LCuX]2; L = TMED, X = Cl, Br or I, L = TEED or TMPD, X = Cl, with the Two Electron Organo Oxidizing Agent, Tetrachloro-1,2-Benzoquinone(TClBQ) in Aprotic Media: Models for Intermediates in Catalytic Catechol Oxidase. Transition Metal Chemistry, 31, 776-781. http://dx.doi.org/10.1007/s11243-006-0067-4
[27]	Gultnokov, G. and Freiser, H. (1968) Heats and Entropies of Formation of Metal Chelates of Certain 8-Quinolonols, Quinoline-8-Thiols, and 2,4-Pentanedione. Analytical Chemistry, 40, 39-44. http://dx.doi.org/10.1021/ac60257a020
[28]	Glowiak, T. and Cizsewska, T. (1978) The Crystal Structure of Bis(S-methyl-N-isopropylidendithiocarbazate)nickel(II). Inorganica Chimica Acta, 27, 27-30. http://dx.doi.org/10.1016/S0020-1693(00)87256-4
[29]	Abo-El-Dahab, H.A. (2009) Kinetics and Mechanism of the Reaction of Bis-(Acetylacetonato) Copper(II) with Bis-(Dithiophosphato) Nickel(II) in Methylene Chloride. Bulletin of the Faculty of Science, Alexandria University, 46, 36-55