Crystal and molecular structure of trans-dithiocyanatobis(N-methyl O-ethylthiocarbamate)palladium(II)

doi:10.1016/S0020-1693(00)89335-4

Inorganica Chimica Acta

Volume 47, 1981, Pages 231-234

https://doi.org/10.1016/S0020-1693(00)89335-4 Get rights and content

Abstract

Trans-dithiocyanatobis(N-methyl O-ethylthiocarbamate)palladium(II) has been prepared and studied by IR and visible spectroscopy. Its molecular structure has been determined from three-dimensional X-ray data. The complex crystallizes in the triclinic system, space group P $1$ with one molecule in a unit cell of dimensions a = 9.522(7), b = 8.352(7), c = 5.658(6) Å, α = 93.1(1), β = 96.5(1), γ = 88.8(1)°. Full-matrix least squares refinement has led the conventional R index (on F) to 0.029 for the 900 observed reflections having I ⩾ 2.5 σ(I). The complex is a typical square-planar Pd(II) species. Relevant structural parameters are: PdS 2.319(1) and 2.331(2) Å S(1)PdS(2) 82.9(1)°.

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Ambidentate ligands, the schizophrenics of coordination chemistry
1990, Coordination Chemistry Reviews
Representative examples of ambidentate ligand chemistry, drawn primarily from studies published during the past decade, are presented. An overview of the physical methods used for structural elucidation is included, with major emphasis being placed on structures emanating from single crystal X-ray diffraction studies. A great variety of ambidentate ligands are covered, although the bulk of the review deals with the schizophrenic behaviour of the classic ambidentate ligands NO₂⁻CN⁻ NCO⁻, NCS⁻ NCSe⁻ and NCTe⁻. As usual, the thiocyanate ion is accorded the most extensive coverage. Other ambidentate ligands discussed include CNO⁻, CNS⁻, azaphospholes, aminobenzonitriles, 4,4'-bipyrimidine, cyanoborohydrides, CCO, ClC(CN)₃, chloranilate ion, isonitroso(β-ketoimine), nicotinate ion, nitramines, nitrosobenzenes and -anilines, Ph₂PC(S)NHR, phosphine/arsine, phosphine sulfide/methine, and phosphinethioamide hybrid ligands, pyridine-2-thione, N-(2-pyridyl)imidazole, 4,6-dimethylpyrimidine, saccharinate ion, H₂NSO₃⁻, SO₃²⁻, Me₂SO, SO₂, SO²⁻, SNO⁻, NSO⁻, S₂O₃₂₋, S₂CO²⁻, SeO₃²⁻, SC(O)NHR⁻, OSNH⁻, dithioimidodiphosphinate ion, dithiosquarate ion, triphosphate ion, and ureas. Transition metal complexes of ambidentate ligands are emphasized throughout the review.
Gold(I) complexes of thio- and dithiocarbamate esters. The structure of bis(N-methyl-O-ethyl-thiocarbamate)gold(I) chloride
1990, Inorganica Chimica Acta
The complexes Au(TMDT)Br, Au(TMDT)Cl, [Au(PPh₃)(TMDT)]NO₃ and Au(MTC)₂Cl (TMDT = N,N-dimethyl-S-methyl-dithiocarbamate, MTC = N-methyl-O-ethyl-thiocarbamate) have been prepared and characterized. The crystal structure of Au(MTC)₂Cl was determined by X-ray crystallography and refined to R = 0.035 based on 2654 observed reflections. The compound is triclinic, space group P $1$ , with a = 6.937(6), b = 9.439(5), c = 12.286(4) Å, α = 74.16(3), β = 99.54(3), γ = 108.06(3)°. The structure consists of Au(MTC)₂⁺ cations significantly distorted from the linear coordination, with a SAuS angle of 155.3(1)° and AuS bond distances of 2.286(2) and 2.284(2) Å, and uncoordinated Cl⁻ anions hydrogen bonded to the two MTC ligands in each cation, with NH···Cl distances of 3.04(1) Å. ¹H NMR spectra of the dithiocarbamate complexes are consistent with coordination of the ligand through its thiocarbonyl sulfur atom.
1. Palladium and platinum
1985, Coordination Chemistry Reviews
Ligating properties of thionitrosoamines. II. Crystal and molecular structure of cis-dichloro-(N-thionitrosodimethylamine)(triphenylarsine)-palladium(II) complex. Synthesis and characterization of neutral binuclear complexes of palladium(II) and cationic complexes of palladium(II) and platinum(II) containing N-thionitrosodimethylamine
1984, Journal of Organometallic Chemistry
The crystal and molecular structure of Pd(SNNMe₂)(AsPh₃)Cl₂ was determined from single-crystal X-ray diffraction data. In agreement with the structure previously proposed on the basis of IR data, the complex has the cis-configuration with the Me₂NNS ligand S-bonded to the metal. It crystallizes in the space group P $1$ with a 9.407(2), b 10.540(2), c 12.265(4) Å; α 68.1(1), β 78.3(1), γ 86.3(1)° and Z = 2. The structure was refined to R = 0.029 for 2664 diffractometer data with I ≥ 3σ(I. The palladium atom is in a nearly square planar coordination geometry with PdS 2.249(1), PdAs 2.362(1), Pd-Cl(1) 2.313(1), PdCl(2) 2.359(1) Å. The very short PdS bond length may indicate a strong σ + π synergistic interaction of the Pd atom with the N-thionitrosodimethylamine ligand. Me₂NNS reacts with Pd(PhCN)₂Cl₂ to give, besides the known cis-Pd(SNNMe2)₂Cl₂, the complex [μ-Cl)₂{Pd(SNNMe₂Cl}₂] (IIIa), and an unstable compound which is probably [Pd(SNNMe₂)₄]Cl₂. The stable salts [Pd(SNNMe₂(BPh₄)₂ (IVa) and [Pd(SNNMe₂)₄]HgCl₄ (IVd) were obtained from this unstable compound and NaBPh₂ or HgCl₄. Alternatively the stable salts [Pd(SNNMe₂)₄](PF₆)₂ (IVb) and [Pd(SNNMe₂)]PdCl₄ (IVc) were obtained from Me₂NNS and [Pd(diene)(acetone)₂](PF₆)₂ (diene = 1,5-cyclooctadiene, norbornadiene) or Na₂PdCl₄. Me₂NNS reacts with Pt(PhCN)₂Cl₂ to form an unstable compound probably [Pt(SNNMe₂)₄]Cl₂ which was obtained in the stable form as [Pt(SNNMe₂)₄]Y₂ (Y = BPh₄ (Va), PF₆ (Vb); Y₂ = PtCl₄ (Vc)). The complexes [(μ-X)₂{Pd(SNNMe₂)Cl}₂] (X = Cl (IIIa), Br (IIIb), SCN (IIIc), SeCN (IIId)) were prepared by reaction of Pd(PhCN)₂Cl₂ with Pd(SNNMe₂)₂X₂.
Ligating properties of thionitrosoamines. I. Neutral mononuclear N-thionitrosodimethylamine-palladium(II) and -platinum(II) complexes
1983, Journal of Organometallic Chemistry
Me₂NNS (Me = methyl) reacts with Pd(diene)Cl₂ (diene = 1,5-cyclooctadiene, norbornadiene, 1,3,5,7-cyclooctatetraene, dicyclopentadiene) to give Pd(Me₂NNS)₂Cl₂ and with M(1,5-cyclooctadiene)Cl₂ (M = Pd^II or Pt^II) in the presence of PR₃ (PR₃ = PPh₃, p-tolylPPh₂) to give M(Me₂NNS)(PR₃)Cl₂. The course of the reactions is, probably, controlled by the chelate effect of the diene. Pd(Me₂NNS)₂Cl₂ reacts with L (L = PPh₃, p-tolylPPh₂, P(o-tolyl)₃, AsPh₃, SbPh₃) to form Pd(Me₂NNS)LCl₂. All the complexes show cis-geometry in the solid state. Me₂NNS brings about bridge-splitting reactions with [Pd(MeO-diene)Cl]₂ (diene = 1,5-cyclooctadiene, 1,3,5,7-cyclooctatetraene, dicyclopentadiene) to form Pd(MeO-diene)(Me₂NNS)Cl. Metathetical reactions with KSCN or KSeCN have been used to prepare Pd(Me₂NNS)₂(XCN)₂ (X = S or Se) and M(Me₂NNS)(PPh₃)(SCN)₂ (M = Pd^II or Pt^II). In all the Me₂NNS complexes the unstable N-thionitrosodimethylamine is S-bonded to the metal and stabilized by this coordination.
Ligating properties of coordinated thiocarboxamido group. Synthesis, crystal and molecular structure of μ-chloro-μ-thiocarboxamidodichlorobis(triphenylphosphine)dipalladium · acetone solvate
1981, Inorganica Chimica Acta
The reaction, in acetone, of the thiocarboxamido complexes [MCI(CSNMe₂)(PPh₃)₂] (M = Pd (1); M = Pt (2)) with some metal halides have been studied. The salts FeCl₃, AlCl₃ and ZnCl₂ react with (1) and (2) to give the dimeric dicationic complexes [M₂(PPh₃)₄(μ-CSNMe₂)]⁺ in which FeCl⁻(in4), AlCl⁻₄ and ZnCl²⁻₄ are the counter ions. The reactions of (1) with HgCl₂, NiCl₂ and PtCl₂ occur with PPh₃ transfer to metal halide and [Pd₂Cl₂(μ-CSNMe₂)₂(PPh₃)₂ and the complexes [Hg(PPh₃)Cl₂]₂, [Ni(PPh₃)₂Cl₂], cis-[Pt(PPh₃)₂Cl₂] respectively are the products. The reactions of (2) with HgCl₂, NiCl₂, PdCl₂ and PtCl₂ proceed analogously. By reacting (1) with PdCl₂ or Na₂PdCl₄ in acetone orange crystals of [Pd₂(PPh₃)₂Cl₂(μ-CsNMe₂)]CH₃COCH₃ are obtained. Analogously [Pd₄(PPh₃)₂Br₂(μ-Br)(μ-CSNMe₂)]CH₃COCH₃ was obtained from the reaction of (1) with Na₂PdBr₄.
The crystal and molecular structure of the title compound has been determined as its acetone solvate by three-dimensional single-crystal X-ray data. The complex crystallizes in the triclinic space group P $1$ in a cell of dimensions a = 16.788(5), b = 12.784(4), c = 10.796(4) Å, α = 98.94(8), β = 101.65(8) and γ = 105.08(7)° with two formula weights corresponding to [(PPh₃)₂Pd₂Cl₃(CSNMe₂]·Me₂CO per unit cell.
The structure was solved by standard heavy-atom methods and refined by least-squares to a final discrepancy factor R of 0.052. In the dimer the two Pd atoms (Pd(1)Pd(2) 3.122(1) Å) are held together through a C(S)NMe bridging ligand (Pd(1)C(37) 1.963(8) Å and Pd(2)S 2.294(2) Å) and an asymmetric chloride bridge (Pd(1)Cl(3) 2.453(2) Å and Pd(2)Cl(3) 2.495(2) Å) and possesses essentially square-planar coordination geometries; the two coordination geometries are completed by two chlorine and two phosphorus atoms from the triphenylphosphine ligands (Pd(1)Cl(1) 2.356(3); Pd(2)Cl(2) 2.330(2); Pd(1)Pd(1) 2.266(3); PdP(2) 2.244(2) Å).
Spectral data of the products are discussed and a possible scheme for the reactions is proposed.

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Crystal and molecular structure of trans-dithiocyanatobis(N-methyl O-ethylthiocarbamate)palladium(II)

Abstract

Inorg. Chim. Acta

Advances in Inorg. Chem. and Radiochem.

Proc. XIX I.C.C.C.,

Svensk. Kem. Tidskr.

Chem. Zentr.

Acta Cryst.

Inorg. Chem.

J. Chem. Soc. Dalton

J. Chem. Soc. Dalton

Inorg. Chem.