Phenylmercury(II) derivatives of tetraorganodichalcogenoimidodiphosphorus acids. Crystal and molecular structure of [PhHg{(OPR2)(SPPh2)N}]2 (R=Me, Ph)

doi:10.1016/j.jorganchem.2003.07.016

Journal of Organometallic Chemistry

Volume 687, Issue 1, 1 December 2003, Pages 118-124

https://doi.org/10.1016/j.jorganchem.2003.07.016 Get rights and content

Abstract

The reactions between PhHgCl or PhHgAc and M[(XPR₂)(YPR′₂)N] (M=Na, K; X, Y=O, S; R, R′=Me, Ph, OEt), in 1:1 molar ratio, have been investigated. PhHg[(XPR₂)(YPR′₂)N] derivatives were isolated as microcrystalline powders and were characterised using IR and NMR (¹H, ¹³C and ³¹P) spectroscopy and mass spectrometry. The molecular structure of PhHg[(OPR₂)(SPPh₂)N] [R=Me (1), Ph (2)] was investigated by X-ray diffraction. In the monomeric unit, PhHg[(OPR₂)(SPPh₂)N], the mercury atom forms the primary bonds with the carbon of the phenyl group and the sulfur atom of the phosphorus ligand [Hg(1)–S(1) 2.405(1) Å for 1, 2.398(2) Å for 2]. These primary bonds are significantly deviated from the expected linear arrangement [C(1)–Hg(1)–S(1) 166.4(2)° for 1, 165.0(2)° for 2]. Both compounds exhibit dimeric associations in the crystal through S,O-bridging organophosphorus ligands [Hg(1)–O(1) 2.556(4) Å for 1, 2.588(4) Å for 2], thus resulting in a distorted T-shaped arrangement of the CHgSO coordination core.. The formation of a 12-membered Hg₂O₂S₂P₄N₂ ring with different conformation in 1 and 2, respectively, results in different additional chalcogen atoms being in the proximity of the metal atom. Weak transannular Hg⋯O [2.753(4) Å] are also established in 1, leading to a tricyclic ladder structure with a planar central Hg₂O₂ ring.

New PhHg[(XPR₂)(YPR′₂)N] derivatives were prepared and were characterized by IR and multinuclear NMR spectroscopy and mass spectrometry. The molecular structure of PhHg[(OPR₂)(SPPh₂)N] [R=Me (1), Ph (2)] was investigated by X-ray diffraction. Both compounds exhibit dimer associations in the crystal through S,O-bridging organophosphorus ligands, resulting in 12-membered inorganic rings of different conformation which brings different additional chalcogen atoms in the proximity of the metal atom. Weak transannular Hg⋯O (2.754 Å) are established in 1, leading to a tricyclic ladder structure with a planar central Hg₂O₂ ring. The CHgSO coordination core has a distorted T-shaped arrangement, with the sulfur atom trans to the aromatic carbon.

Introduction

The large bite and high flexibility of the tetraorganodichalcogenoimidodiphosphorus anions make them versatile ligands towards metallic and organometallic centers. A variety of structures has been reported for complexes of Main Group elements, including Group 12 metals, due to the coordination opportunities offered both by metals and ligands [1]. Only a few mercury(II) compounds containing imidodiphosphorus ligands, i.e. inorganic Hg[(SPPh₂)₂N]₂, HgCl[(SPPh₂)₂N] [2], Hg[(SePPh₂)₂N]₂ [3], and organometallic derivatives, i.e. PhHg[{OP(OPh)₂}₂N] [4], [5], are known. The inorganic species Hg[(SePPh₂)₂N]₂ was found to exhibit a spiro NP₂Se₂HgSe₂P₂N core with tetrahedral coordinated metal center due to the expected Se,Se-chelating nature of the ligand moieties [3]. By contrast, unusual N,O-bridging imidodiphosphorus ligands led to dimeric species in the crystal of PhHg[{OP(OPh)₂}₂N] (Fig. 1a). The reaction of HgO with [OP(OPh)₂]₂NH or (OPEt₂}[OP(OPh)₂]NH resulted in ortho-mercuration of a phenoxy group and isolation of dinuclear compounds, Hg₂[(OPR₂){OP(OPh)(OC₆H₄-2)}N]₂ (R=Et [6], OPh [4]) (Fig. 1b). The second covalence at the mercury atom is achieved through a Hg-N bond which involves the nitrogen of a neighboring mercurated imidodiphosphoric ligand, thus resulting in the formation of a 12-membered Hg₂C₄O₂P₂N₂ ring with almost linear N–Hg–C fragments.

In the context of our interest in the coordination chemistry of imidodiphosphorus ligands [1], we decided to investigate the influence of the nature of the chalcogen atoms in organomercury(II) derivatives containing ligands of the type [(XPR₂)(YPR′₂)N]⁻. We report here on the synthesis and spectroscopic characterization of some phenylmercury(II) compounds, PhHg[(XPR₂)(YPR′₂)N], as well as the crystal and molecular structure of PhHg[(OPR₂)(SPPh₂)N] [R=Me, Ph].

Section snippets

Preparation

The title compounds were prepared according to Eq. (1), by reacting stoichiometric amounts of either phenylmercury(II) chloride or acetate and the alkali salt of the appropriate tetraorganodichalcogenoimidodiphosphorus ligand:

All compounds were isolated as air-stable, colorless crystalline products. They were characterized by multinuclear (¹H, ¹³C and ³¹P) NMR and IR spectroscopy and mass spectrometry. The crystal and molecular structures of PhHg[(OPMe₂)(SPPh₂)N] (1) and PhHg[(OPPh₂)(SPPh₂)N] (2

Conclusions

New PhHg[(XPR₂)(YPR′₂)N] (X, Y=O, S; R, R′=Me, Ph, OEt) derivatives were prepared and characterized using IR and NMR (¹H, ¹³C and ³¹P) spectroscopy and mass spectrometry. Evidence for the presence of dimeric associations was obtained from MS data. The molecular structure of PhHg[(OPR₂)(SPPh₂)N] [R=Me (1), Ph (2)] was investigated by X-ray diffraction. Both compounds exhibit dimeric associations in the crystal through S,O-bridging organophosphorus ligands, resulting in 12-membered inorganic

Materials and procedures

The starting materials were prepared according to literature methods: Na[(OPMe₂)(SPPh₂)N], [8] K[(OPPh₂)(SPPh₂)N] [7], K[{OP(OEt₂)}(SPPh₂)N], [9] K[{OP(OEt₂)}(OPPh₂)N] [9], PhHgCl and PhHgO(O)CCH₃ [16]. Solvents were dried on potassium (toluene) and sodium (n-hexane) and freshly distilled prior to use. Infrared spectra were recorded in the range 4000–250 cm⁻¹ as KBr pellets on a Jasco FT/IR-615 instrument. The ¹H-, ¹³C- and ³¹P-NMR spectra were recorded on a VARIAN GEMINI 300S instrument

Supplementary material

Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Centre, CCDC nos. 197677 and 197678 for compounds 1 and 2, respectively. Copies of this information may be obtained free of charge from The Director, CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax: +44-1223-336033; e-mail: [email protected] or www: http://www.ccdc.cam.ac.uk).

Acknowledgements

This work was supported by the National University Research Council of Romania (CNCSIS). M.B.H. thanks the UK Engineering and Physical Sciences Council for support of the X-ray facilities at Southampton. J.E.D. thanks the Natural Sciences and Engineering Research Council of Canada for financial support.

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Journal of Organometallic Chemistry

Abstract

Introduction

Section snippets

Preparation

Conclusions

Materials and procedures

Supplementary material

Acknowledgements

References (21)

Coord. Chem. Rev.

Inorg. Chim. Acta

Inorg. Chim. Acta

J. Organomet. Chem.

Polyhedron

J. Organomet. Chem.

Z. Naturforsch. Teil B

Z. Anorg. Allg. Chem.

Cited by (12)

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