Crystal and molecular structure of spirobicyclic bis(tetraphenyldithioimidodiphosphinato)lead(II), [Pb(SPPh2)2N];2], containing a new inorganic (carbon-free) PbS2P2N chelate ring and Pb(η6-C6H5) interactions

doi:10.1016/S0277-5387(00)86619-X

Polyhedron

Volume 13, Issue 20, October 1994, Pages 2873-2879

https://doi.org/10.1016/S0277-5387(00)86619-X Get rights and content

Abstract

The title compound, [PbSPPh₂)₂N];₂], was obtained by reacting potassium tetraphenyldithioimidodiphosphinate with lead(II) acetate. X-ray diffraction analysis reveals an unsymmetrical (anisobidentate) coordination of the chelating ligands, indicated by non-equal PbS interatomic distances [2.695(4) and 2.943(4) Å] and some PN and PS bond length alternation within the two NP₂S₂Pb rings that form the spirobicyclic complex. The lead coordination is supplemented by two additional Pb(η⁶-C₆H₅) interactions with two phenyl groups. If these interactions are considered, the geometry of the coordination sphere may be described as distorted octahedral.

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Non-rigid coordination behavior of the ambidentate phosphinoyldithioformate ligands, [S<inf>2</inf>CP(O)R<inf>2</inf>]<sup>-</sup>, (R = Ph, CH<inf>2</inf>Ph) in organometallic Lead(IV) and Mercury(II) compounds
2018, Journal of Organometallic Chemistry
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The Pb-S bond distances of 2.739(1) and 2.769(1) Å are comparable to bond distances found for sulfur ligands in the octahedral organometallic lead(IV) compounds, [Ph2Pb(S2P(OBz)2)2] (2.679, 2.723 Å) [10] and [Ph2Pb(S2PPh2)2] (2.656 Å).4(d) However, the Pb-S bond distances in 1 are somewhat longer than the Pb-S bond distances in the [Ph2Pb(L1)2] octahedral compound that has Pb-S bond distances of 2.704(1) and 2.714(1) Å, presumably because of the larger coordination number of the lead atom in 1 [16]. The Pb-O(1) and Pb-O(2) bond lengths of 2.435(5) and 2.488(8) Å are comparable to the Pb-O bond distances found in Ph2Pb[(OPPh2)2N]2 and Me2Pb[(OPPh2)2N]2 (2.342(5) - 2.462(5) Å) [21], and compare well with distances observed in the octahedral structure of 1 [12]. The coordinated L2 shows considerable single bond character for the P-O bonds with bond distances of 1.506(1) and 1.507(1) Å indicating significant donation from oxygen atoms to the lead center.
A series of phosphinoyldithioformate compounds were synthesized from metathesis reactions of K[R₂P(O)CS₂], and R'_nPbCl_4-n and R’HgCl. The compounds isolated were characterized using infrared, UV and multinuclear NMR (¹H, ¹³C, and ³¹P) spectroscopy. Structural diversity of these compounds is revealed through analysis of the infrared and NMR spectroscopy, where variable temperature ³¹P NMR spectroscopy data of 6 reveals non-rigid coordination behavior and an equilibrium of aniso bonded S,S 4-membered ring, and S,O bonded 5-membered ring bonding modes in [MeHg{S₂CP(O)(Ph)₂}], (6–6′). The crystal structure of 6′ shows the mercury atom in a T-shape geometry with S,O-bidentate coordinated ligand although room temperature NMR indicated the coordination to the mercury in 6 is non rigid in solution. Variable temperature ³¹P NMR spectroscopy yielded an average value of ΔG^#_6-6´ = 45.7 ± 1.7 kJ mol⁻¹ for the temperature range of 190 K–283 K. The crystal structure of [Ph₂Pb{S₂CP(O)(Ph)₂}₂(H₂O)], 1, reveals the lead atom in an unusual seven coordinate geometry with two S,O-bidentate coordinated ligands and axial phenyl groups. The seventh ligand is a water molecule bonded to lead forming a pentagonal plane.
The use of sacrificial anodes for the electrochemical synthesis of metallic complexes
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So, the electrolysis of HL84b with an anode of this metal gave the complex [Pb(L84b)2], where the lead atom is coordinated by two bidentate monoanionic ligands. The arrangement of the molecules in the crystal cell let the phenyl ring to be in the hood of a lead atom; so a weak Pb-(η6-C6H5) interaction is achieved between the lone electronic pair located in the equatorial plane and the ring [261–263]. Heterocyclic thioamides are another kind of sulfur donor proligand.
In this work, a compilation of electrochemically prepared metallic complexes is presented. All of them were synthesized by using a single step electrolytic process. This procedure is useful in the syntheses of homoleptic and heteroleptic complexes. Perhaps the most important point is the versatility of the proligands which can be used for the syntheses: a variety of functional groups and a number of coordination modes for the different ligands are reported.
However, unpredictable results were also obtained in some cases; these results were successfully interpreted and, many times, they were useful for new syntheses, both by using the results themselves or for the prevention against non desirable products. A summary of these unexpected situations is also presented.
Tin and lead phosphinothiolate derivatives. Crystal structures of [Ph <inf>3</inf>Sn{Ph<inf>2</inf>PC<inf>6</inf>H<inf>4</inf>S-2}], [Sn{PhP(C <inf>6</inf>H<inf>4</inf>S-2)<inf>2</inf>}<inf>2</inf>] and [Pb{Ph <inf>2</inf>P(O)C<inf>6</inf>H<inf>4</inf>S-2}<inf>2</inf>]·1/2CH <inf>3</inf>OH·2H<inf>2</inf>O complexes
2014, Journal of Organometallic Chemistry
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The average value of the distances between the lead atom and the carbon atoms of this phenyl group is 4.117 Å, with a value of 3.958 Å for the distance to the center of the ring. This value is slightly shorter than the sum of the van der Waals radii, 3.70 Å, when the radius of the phenyl group is considered in the direction perpendicular to the phenyl ring [33]. Interactions of the type Pb–(η6-C6H5) have also been found in the case of [Pb{S(PPh2)2N}2] [34] and [Pb{S2P(OPh)2}2] [35] complexes.
The coordination capability of the phosphinothiol ligands Ph₂PC₆H₄SH-2 and PhP(C₆H₄SH-2)₂, towards two organotin (Ph₃SnCl, Ph₂SnCl₂) and the organolead Ph₂PbCl₂ was studied. The complexes were characterized by microanalysis, FAB mass spectrometry, IR and NMR spectroscopy. Also, crystal structures of [Ph₃Sn{Ph₂PC₆H₄S-2}], [Sn{PhP(C₆H₄S-2)₂}₂] and [Pb{Ph₂P(O)C₆H₄S-2}₂]·1/2CH₃OH·2H₂O complexes have been determined. The structure of [Ph₃Sn{Ph₂PC₆H₄S-2}] complex shows the triphenyltin fragment coordinated to one monoanionic phosphinothiol ligand acting as monodentate through the thiolate sulfur atom with the tin ion in a tetrahedral environment. The crystal structure of [Sn{PhP(C₆H₄S-2}₂] shows the metal ion in a distorted octahedral geometry. The geometry about the Pb in [Pb{Ph₂P(O)C₆H₄S-2}₂]·1/2CH₃OH·2H₂O complex is best described as distorted ψ−trigonal bipyramidal with the five position occupied by the active lone pair of metal. Intermolecular weak Pb-(η⁶-C₆H₅) interactions between the lead electron pair and phenyl rings are also observed.
Stereochemistry of lead(II) complexes containing sulfur and selenium donor atom ligands
2010, Coordination Chemistry Reviews
The stereochemistry of lead(II) complexes with S- and Se-donor atom ligands, including mixed ligand complexes is reviewed with respect to the geometry of the first coordination sphere of the Pb(II) atom in these compounds and rationalized in terms of the valence shell electron-pair repulsion (VSEPR) model. The most comprehensively structurally characterized classes of lead(II) thio and seleno complexes are discussed, including monothio-, dithio(seleno)-, trithio- and tetrathio-complexes, as well as Pb(II) dialkyldithio(seleno)carbamates, alkylxanthates and dialkyl(aryl) phosphorodithio(seleno)lates. Data about the polyhedral shape of the primary coordination sphere, coordination number (CN), bond lengths (primary and secondary) and bond angles of the Pb(II) atom in the compounds under investigation are systematized in comprehensive tables. The particularities of the stereochemistry of Pb(II) complexes with S(Se)-donor atom ligands are comparatively discussed with the stereochemistry of lead(II) complexes with oxygen donor ligands.
β-Functionalized ethylchalcogenolate complexes of lead(II): Synthesis, structures and their conversion into lead chalcogenide nanoparticles
2009, Polyhedron
The reactions of Pb(OAc)₂·3H₂O with NaER yield homoleptic colorless to yellow complexes of composition, [Pb(ER)₂] (ER = SCH₂CH₂NMe₂ (1), SeCH₂CH₂NMe₂ (2) and SeCH₂CH₂COOMe (3)). These complexes were characterized by elemental analyses, UV–Vis and ¹H NMR data. Molecular structures of [Pb(ECH₂CH₂NMe₂)₂] (E = S or Se) have been established by single crystal X-ray diffraction analyses. These molecules have a distorted trigonal bipyramidal configuration around lead with the nitrogen atoms of the chelating chalcogenolate ligands occupying the axial positions. Thermal behavior of these complexes was studied by TG analysis. Pyrolysis in a furnace or in HDA (hexadecylamine) gave PbE nanoparticles which were characterized by UV–Vis, photoluminescence, XRD, EDAX, and TEM measurements.
Lead(II) Coordination Chemistry in the Solid State
2006, Lead: Chemistry, Analytical Aspects, Environmental Impact and Health Effects
This chapter deals with the coordination chemistry of lead in the solid state, a particularly fascinating field that has experienced clear resurgence in the past few decades. The numerous applications of the metal in technology, its widespread occurrence in the environment, and public concern about its toxic effects have markedly increased the attention paid to its interaction with both natural and non-natural ligands. Most of the inorganic chemistry of lead is associated with its oxidation state. The few compounds containing Pb(IV) that have been well characterized are all strong oxidizing agents. The opposite is true in organolead chemistry. This rather striking division has been traditionally associated with the "inert-pair effect" and, more recently, to the differences in the radial extension of s- and p-orbitals when electronegative substituents are bound to the metal. If these differences increase, the spⁿ hybridization becomes more unfavorable, the Pb-X bonds become weaker, and the oxidation state becomes more unstable.

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¹: European Community Visiting Scientist from Universitatea ‘Babes-Bolyai’, Facultatea de Chimie, RO-3400 Cluj-Napoca, Romania.

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Crystal and molecular structure of spirobicyclic bis(tetraphenyldithioimidodiphosphinato)lead(II), [Pb(SPPh2)2N];2], containing a new inorganic (carbon-free) PbS2P2N chelate ring and Pb(η6-C6H5) interactions

Abstract

Coord. Chem. Rev.

Inorg. Chem.

Z. Naturfor.

Acta Chem. Scand.

Inorg. Chim. Acta

Inorg. Chem.

Inorg. Chem.

Monatsh. Chem.

Inorg. Chem.

Rev. Inorg. Chem.

Z. Anorg. Allg. Chem.

Synth. React. Inorg. Metal-Org. Chem.

Polyhedron

Crystal and molecular structure of spirobicyclic bis(tetraphenyldithioimidodiphosphinato)lead(II), [Pb(SPPh₂)₂N];₂], containing a new inorganic (carbon-free) PbS₂P₂N chelate ring and Pb(η⁶-C₆H₅) interactions