Isomerism in bis(phenylselenolato)bis(triphenylphosphine)platinum(II): the crystal and molecular structures of cis- and trans-[Pt(SePh)2(PPh3)2]

doi:10.1016/S1387-7003(00)00091-5

Inorganic Chemistry Communications

Volume 3, Issue 7, July 2000, Pages 397-399

https://doi.org/10.1016/S1387-7003(00)00091-5 Get rights and content

Abstract

The reaction of cis-[PtCl₂(PPh₃)₂] and NaSePh in benzene produces a mixture of cis- and trans-isomers of the monomeric platinum complex [Pt(SePh)₂(PPh₃)₂]. The low-temperature X-ray structures of both isomers are reported. The structure of cis-[Pt(SePh)₂(PPh₃)₂] is the first crystallographic characterized cis-isomer of mononuclear platinum(II) complex containing only non-chelating organoselenolato and phosphine ligands.

Introduction

Mononuclear platinum complexes containing selenolato ligands ^–SeR can conveniently been prepared by the oxidative addition of organic diselenides R₂Se₂ to Pt(0) centers or by the reaction of NaSeR with halogenated Pt(II) complexes [1]. Whereas the formation of cis- and trans-[Pt(SeR)₂(PPh₃)₂] (R=Ph, phenyl or Th, thienyl) from Pt(0) or Pt(II) has been well-established in solution [2], [3], [4], [5], [6], [7], the X-ray structures have only been known for the trans-isomers [2], [3], [4]. In this work we report the low-temperature crystal structure of cis-[Pt(SePh)₂(PPh₃)₂] and compare its structural characteristics with those of the trans-isomer. To our knowledge, this is the first time that the solid state structure of a cis-isomer of a mononuclear selenolatoplatinum complex containing only non-chelating ligands is described [8]. We also discuss the solution equilibrium between the two isomers.

Section snippets

Experimental

The preparation of [Pt(SePh)₂(PPh₃)₂] was carried out under a dry argon atmosphere by adding 1.30 mmol of NaSePh {prepared in situ by the reduction of 202 mg (0.65 mmol) Ph₂Se₂ (Aldrich) in benzene with NaBH₄ in methanol} into the suspension of 511 mg (0.65 mmol) cis-[PtCl₂(PPh₃)₂] (Aldrich) in benzene. Otherwise, the procedure followed that described previously [3], [4], [6]. The crystals of cis-[Pt(SePh)₂(PPh₃)₂]·C₆H₆ (1) and trans-[Pt(SePh)₂(PPh₃)₂ (2) suitable for X-ray analysis were

Results and discussion

The reaction of cis-[PtCl₂(PPh₃)₂] with NaSePh affords [Pt(SePh)₂(PPh₃)₂]. Both the ³¹P and ¹⁹⁵Pt NMR spectra recorded for the reaction mixture exhibit two resonances and indicate that the reaction produces both cis- and trans-isomers. The ³¹P resonances at 19.1 and 20.8 ppm are assigned to cis- and trans-isomers, respectively, on the basis of previous spectroscopic data for [Pt(SePh)₂(PPh₃)₂] [3], [4] and [Pt(SeTh)₂(PPh₃)₂] [2]. The corresponding ¹⁹⁵Pt resonances for the cis- and trans

Supplementary material

Crystallographic information of the complexes 1 and 2 have been deposited with the Cambridge Crystallocraphic Data Center as supplementary publication numbers CCDC 142345 and CCDC 142346.

Acknowledgements

Financial support from Neste Oy Foundation and Academy of Finland is gratefully acknowledged.

References (12)

R. Oilunkaniemi et al.
J. Organomet. Chem.
(1999)
H. Gysling, in: S. Patai, Z. Rappoport, The Chemistry of Organic Selenium and Tellurium Compounds, vol. I, Wiley, New...
V.K. Jain, S. Kannan, E.R.T. Tiekink, J. Chem. Res. (S) (1994)...
V.K. Jain, S. Kannan, E.R.T. Tiekink, J. Chem. Res. (M) (1994)...
V.W. Day et al.
J. Am. Chem. Soc.
(1982)
S.K. Gupta et al.
Indian J. Chem.
(1990)

There are more references available in the full text version of this article.

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The oxidative addition reaction of ditellurides R₂Te₂ [R = ⁿBu, Ph, Th (2-thienyl, C₄H₃S)] to [Pt(η²-nb)(dppn)] (nb = norbornene, dppn = 1,2-bis(diphenylphosphano)naphthalene) was found to afford [Pt(TeR)₂(dppn)] [R = ⁿBu (1), Ph (2), Th (3)] and [Pt(TeR)(R)(dppn)] [R = Ph (4), Th (5)] as a result of the cleavage of the Te-Te or C-Te bond, respectively. The reactions and the product distributions were monitored by ³¹P{¹H} NMR spectroscopy. The spectral interpretation was assisted by the high-yield preparation of [Pt(TePh)₂(dppn)] (2) and [Pt(TeTh)₂(dppn)] (3) by ligand exchange reactions from [PtCl₂(dppn)], and by the crystal structure determinations and spectral characterizations of 2 and 3. Two series of reactions were carried out both at room temperature and at −80 °C. One involved the addition of the toluene solution of R₂Te₂ to that of [Pt(η²-nb)(dppn)], and the other the addition of [Pt(η²-nb)(dppn)] solution to the R₂Te₂ solution. The oxidative addition of ⁿBu₂Te₂ to [Pt(η²-nb)(dppn)] yielded solely [Pt(TeⁿBu)₂(dppn)]. In case of Ph₂Te₂ and Th₂Te₂, the reaction of equimolar amounts of ditelluride and [Pt(η²-nb)(dppn)] afforded only [Pt(TeR)(R)(dppn)] (R = Ph, Th), but when an excess of R₂Te₂ was used, the addition of [Pt(η²-nb)(dppn)] to the ditelluride resulted in the formation of a mixture of [Pt(TeR)₂(dppn)] and [Pt(TeR)(R)(dppn)] with the latter the main component. An excess of R₂Te₂ and the lowering of the temperature favoured the formation of [Pt(TeR)₂(dppn)]. The reaction energetics in toluene was calculated at revPBE/def2-TZVP(-f) level of theory. The increase of the electron withdrawing nature of the organic substituent rendered [Pt(TeR)(R)(dppn)] increasingly stable with respect to [Pt(TeR)₂(dppn)]. The computation of the energy profiles of the likely pathways of the oxidative addition indicated that concurrent formation of [Pt(TeR)₂(dppn)] and [Pt(TeR)(R)(dppn)] (R = Ph, Th) may be more likely than the formation of the latter due to the decomposition of the former. This was verified experimentally by stirring pure [Pt(TeR)₂(dppn)] in toluene for a prolonged time at room temperature. No decomposition was observed.
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2012, Journal of Organometallic Chemistry
Citation Excerpt :
The Pt–P distances are in good agreement with those reported for [Pt(SeR′)2(PR3)2] complexes [17,18,35]. The two acute (82.74(5)°) and obtuse (97.26(5)°) P–Pt–Se angles can be compared with trans-[Pt(SeTh)2(PPh3)2] (∼83 and ∼96°), but differ from phenylselenolate derivatives, trans-[Pt(SePh)2(PR3)2] (R = Et, Bu, Ph) (∼86 and ∼94°) [18,35,37]. The palladium atom in 3a acquires distorted square planar geometry defined by P, N, Se2 donor atoms, the neutral donor atoms (P and N) being trans.
Oxidative addition reactions of {SeC₄H(4,6-R)₂N₂}₂ with [M(PPh₃)₄] (M = Pt or Pd) in benzene afforded complexes of composition, [Pt{SeC₄H(4,6-R)₂N₂}₂(PPh₃)₂] (1) and [Pd{η²-SeC₄H(4,6-R)₂N₂}{SeC₄H(4,6-R)₂N₂}(PPh₃)] (3) (R = H or Me). The former when left in solution dissociated to [Pt{η²-SeC₄H(4,6-R)₂N₂}{SeC₄H(4,6-R)₂N₂}(PPh₃)] (2) and PPh₃. Treatment of [PtCl₂(P^∩P)] (P^∩P = dppe or dppp) and NaEC₄H(4,6-R)₂N₂ (for E/R = Se/H/Me or Te/Me) gave mononuclear complexes [Pt{EC₄H(4,6-R)₂N₂}₂(P^∩P)] (4 and 6) (R = H or Me, P^∩P = dppe or dppp) which on leaving for recrystallization in dichloromethane/CDCl₃ solution resulted in trinuclear chalcogenido-bridged complexes [Pt₃(μ-E)₂(P^∩P)₃]·2Cl (E = Se or Te) (6). The latter were also formed when [PtCl₂(P^∩P)] (P^∩P = dppe or dppp) was treated with sodium 2-pyrimidyltellurolate. The substitution reactions between [PdCl₂(P^∩P)] (P^∩P = dppe or dppp) and NaEC₄H(4,6-R)₂N₂ (E = Se or Te; R = H or Me) afforded chalcogenido-bridged trinuclear complexes, [Pd₃(μ-E)₂(P^∩P)₃]2Cl (7) (P^∩P = dppe or dppp). These complexes were characterized by elemental analyses and NMR (¹H, ³¹P, ⁷⁷Se, ¹²⁵Te, ¹⁹⁵Pt) spectroscopy. The molecular structures of [Pt(SeC₄H₃N₂)₂(PPh₃)₂] (1a) and [Pd{η²-SeC₄H₃N₂}{SeC₄H₃N₂}(PPh₃)] (3a) were established by single crystal X-ray diffraction analyses. Metal atom in these complexes acquires a distorted squareplanar configuration.
Synthesis and spectroscopy of cis-configured mononuclear palladium(II) and platinum(II) complexes of chalcogeno o-carboranes and structures of [Pt(SCb oPh)<inf>2</inf>(dppm)], [Pt(SeCboPh)<inf>2</inf>(dppm)], [Pt(SCboS)(PMe<inf>2</inf>Ph)<inf>2</inf>] and [Pt(SCb oS)(PMePh<inf>2</inf>)<inf>2</inf>]
2012, Journal of Organometallic Chemistry
Citation Excerpt :
These include (i) use of chelating phosphine ligands [16], (ii) chelating thiolate ligands (S-R-S)2− [17,18], (iii) bulky chalcogenolate ligands [19,20] and internally functionalized chalcogenolate ligands [5,21–23]. Monomeric complexes, [M(SR)2(PR3)2] have been studied with reference to cis- and trans-isomerization process [24] and in fact the cis isomer is readily isomerized to trans form in solution [24–28]. The DFT calculations on model complexes, [Pt(SeR)2(PH3)2] revealed that the cis isomers lie at higher energy than that of the trans isomer [25].
The reactions of [MCl₂(P^∩P)] and [MCl₂(PR₃)₂)] with 1-mercapto-2-phenyl-o-carborane/NaSeCb^oPh and 1,2-dimercapto-o-carborane yield mononuclear complexes of composition, [M(SCb^oPh)₂(P^∩P)], [M(SeCb^oPh)₂(P^∩P)] (M = Pd or Pt; P^∩P = dppm (bis(diphenylphosphino)methane), dppe (1,2-bis(diphenylphosphino)ethane) or dppp (1,3-bis(diphenylphosphino)propane)) and [M(SCb^oS)(PR₃)₂] (2PR₃ = dppm, dppe, 2PEt₃, 2PMe₂Ph, 2PMePh₂ or 2PPh₃). These complexes have been characterized by elemental analysis and NMR (¹H, ³¹P, ⁷⁷Se and ¹⁹⁵Pt) spectroscopy. The ¹J(Pt–P) values and ¹⁹⁵Pt NMR chemical shifts are influenced by the nature of phosphine as well as thiolate ligand. Molecular structures of [Pt(SCb^oPh)₂(dppm)], [Pt(SeCb^oPh)₂(dppm)], [Pt(SCb^oS)(PMe₂Ph)₂] and [Pt(SCb^oS)(PMePh₂)₂] have been established by single crystal X-ray structural analyses. The platinum atom in all these complexes acquires a distorted square planar configuration defined by two cis-bound phosphine ligands and two chalcogenolate groups. The carborane rings are mutually anti in [Pt(SCb^oPh)₂(dppm)] and [Pt(SeCb^oPh)₂(dppm)].
NMR approach for the identification of dinuclear and mononuclear complexes: The first detection of [Pd(SPh)<inf>2</inf>(PPh<inf>3</inf>)<inf>2</inf>] and [Pd<inf>2</inf>(SPh)<inf>4</inf>(PPh<inf>3</inf>)<inf>2</inf>] - The intermediate complexes in the catalytic carbon-sulfur bond formation reaction
2011, Journal of Organometallic Chemistry
In the present study we have analyzed the nature of palladium complexes in the catalytic system for selective carbon–sulfur bond formation via the addition of S–S and S–H bonds to alkynes. For the first time the mononuclear and dinuclear palladium complexes were clearly detected by DOSY NMR under the catalytic conditions. It was demonstrated that the concentration of these palladium complexes strongly depends on the amount of phosphine ligand available under reaction conditions.
Structural and spectroscopic trends in mononuclear arylchalcogenolato-palladium(II) and -platinum(II) complexes: Crystal structures of [M(TeAr)<inf>2</inf>(dppe)] {M = palladium, platinum; Ar = phenyl, 2-thienyl; dppe = 1,2-bis(diphenylphosphino)ethane}
2007, Journal of Organometallic Chemistry
A series of mononuclear [M(EAr)₂(dppe)] [M = Pd, Pt; E = Se, Te; Ar = phenyl, 2-thienyl; dppe = 1,2-bis(diphenylphosphino)ethane] complexes has been prepared in good yields by the reactions of [MCl₂(dppe)] and corresponding ArE⁻ with a special emphasis on the aryltellurolato palladium and -platinum complexes for which the existing structural information is virtually non-existent. The complexes have crystallized in five isomorphic groups: (1) [Pd(SePh)₂(dppe)] and [Pt(SePh)₂(dppe)], (2) [Pd(TePh)₂(dppe)] and [Pt(TePh)₂(dppe)], (3) [Pd(SeTh)₂(dppe)], (4) [Pt(SeTh)₂(dppe)] and [Pd(TeTh)₂(dppe)], and (5) [Pt(TePh)₂(dppe)]. In addition, solvated [Pd(TePh)₂(dppe)] · CH₃OH and [Pd(TeTh)₂(dppe)] · 1/2CH₂Cl₂ could be isolated and structurally characterized. The metal atom in each complex exhibits an approximate square-planar coordination. The Pd–Se, Pt–Se, Pd–Te, and Pt–Te bonds span a range of 2.4350(7)–2.4828(7) Å, 2.442(1)–2.511(1) Å, 2.5871(7)–2.6704(8) Å, and 2.6053(6)–2.6594(9) Å, respectively, and the respective Pd–P and Pt–P bond distances are 2.265(2)–2.295(2) Å and 2.247(2)–2.270(2) Å. The orientation of the arylchalcogenolato ligands with respect to the M(E₂)(P₂) plane has been found to depend on the E–M–E bond angle. The NMR spectroscopic information indicates the formation of only cis-[M(EAr)₂(dppe)] complexes in solution. The trends in the ³¹P, ⁷⁷Se, ¹²⁵Te, and ¹⁹⁵Pt chemical shifts expectedly depend on the nature of metal, chalcogen, and aryl group. Each trend can be considered independently of other factors. The ⁷⁷Se or ¹²⁵Te resonances appear as second-order multiplets in case of palladium and platinum complexes, respectively. Spectral simulation has yielded all relevant coupling constants.
Oxidative addition of (PhSe)<inf>2</inf> and (FcSe)<inf>2</inf> to zerovalent palladium and platinum trialkylphosphine complexes (Fc = ferrocenyl, [Fe(η5-C<inf>5</inf>H<inf>5</inf>)(η5-C<inf>5</inf>H<inf>4</inf>)])
2006, Journal of Organometallic Chemistry
Room temperature reaction of [Pd₂(dba)₃]/PR₃ or [Pt(C₂H₄)(PR₃)₂] (dba = dibenzylideneacetone; R = Et, Bu) with the diselenides (R′Se)₂ (R′ = Ph, Fc) yielded the oxidative addition products trans-[M(SeR′)₂(PR₃)₂] (M = Pd, Pt). These have been characterised by multinuclear NMR and UV–Vis spectroscopy, mass spectrometry, and, in the cases of trans-[Pt(SePh)₂(PR₃)₂] (R = Et, Bu) and trans-[Pt(SeFc)₂(PBu₃)₂], also by X-ray crystallography.

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Inorganic Chemistry Communications

Abstract

Introduction

Section snippets

Experimental

Results and discussion

Supplementary material

Acknowledgements

References (12)

J. Organomet. Chem.

J. Am. Chem. Soc.

Indian J. Chem.

Cited by (37)

Competitive Te-Te and C-Te bond cleavage in the oxidative addition of diaryl and dialkyl ditellurides to Pt(0) centers

Reactivity of dipyrimidyldiselenides with [M(PPh <inf>3</inf>) <inf>4</inf>] and 2-pyrimidylchalcogenolates with [MCl <inf>2</inf>(diphosphine)] (M = Pd or Pt)

NMR approach for the identification of dinuclear and mononuclear complexes: The first detection of [Pd(SPh)<inf>2</inf>(PPh<inf>3</inf>)<inf>2</inf>] and [Pd<inf>2</inf>(SPh)<inf>4</inf>(PPh<inf>3</inf>)<inf>2</inf>] - The intermediate complexes in the catalytic carbon-sulfur bond formation reaction

Structural and spectroscopic trends in mononuclear arylchalcogenolato-palladium(II) and -platinum(II) complexes: Crystal structures of [M(TeAr)<inf>2</inf>(dppe)] {M = palladium, platinum; Ar = phenyl, 2-thienyl; dppe = 1,2-bis(diphenylphosphino)ethane}

Oxidative addition of (PhSe)<inf>2</inf> and (FcSe)<inf>2</inf> to zerovalent palladium and platinum trialkylphosphine complexes (Fc = ferrocenyl, [Fe(η<sup>5</sup>-C<inf>5</inf>H<inf>5</inf>)(η<sup>5</sup>-C<inf>5</inf>H<inf>4</inf>)])