Paul F. Kelly

The preparation and structure of complexes containing simple sulphur-nitrogen ligands

Complexes avec les groupes NS, NSX, les diimines, complexes de S 2 N 2 H − , S 2 N 2 2− , S 3 N − et S 2 N 3 3−

Fingerprint and inkjet-trace imaging using disulfur dinitride

Exposure of fingerprints to S(2)N(2) vapour results in the prints being visually imaged by polymeric (SN)(x) on an unprecedented range of media; in addition, the polymer forms in response to the interaction of S(2)N(2) with traces of inkjet inks, for example the minute amounts left by the contact between printed paper and an envelope.

Preparation of a range of copper complexes of diphenylsulfimide: X-ray crystal structures of [Cu(Ph2SNH)4]Cl2 and [Cu4(μ4-O)(μ-Cl)6(Ph2SNH)4]

Abstract Reaction of Ph 2 SNH 1 with CuCl 2 (molar ratio 2:1) in acetonitrile gives trans -[CuCl 2 (Ph 2 SNH) 2 ] 2a which may be isolated as blue crystals (square planar form) by crystallisation from hot MeCN or as green needles (pseudo-tetrahedral form) by slow evaporation of a CH 2 Cl 2 /petroleum ether solution. In contrast, [CuBr 2 (Ph 2 SNH) 2 ] 2b , most efficiently prepared by reaction of [Cu(Ph 2 SNH) 4 ]Br 2 with CuBr 2 , appears to only exist in a dark green, pseudo-tetrahedral form. When 1.5 equivalents of 1 are reacted with CuX 2 in air, [Cu 4 (μ 4 -O)(μ-X) 6 (Ph 2 SNH) 4 ] (X=Cl 3a or Br 3b ) forms as orange crystals. X-ray crystallography reveals 3a to have the expected tetrahedral arrangement of Cu atoms within an oxo-centered Cu 4 Cl 6 O core. Four equivalents of 1 react with CuX 2 to give purple [Cu(Ph 2 SNH) 4 ]X 2 (X=Cl 4a or Br 4b ); the X-ray crystal structure of 4a reveals a square planar structure exhibiting strong hydrogen bonding interactions between the ligands and the counterions. Even in the presence of excess 1 , no more than four of the ligands may be added to a copper centre.

The preparation and X-ray structure of PtCl2(S4N4)(PMe2Ph), an octahedral complex containing a meridional tridentate S4N42− ligand

Abstract Reaction Of [PtCl 2 (PMe 2 Ph)] 2 ( 1 ) with S 4 N 4 in CH 2 Cl 2 leads to the platinum(IV) complex PtCl 2 (S 4 N 4 )(PMe 2 Ph) ( 2 ), which contains the tridentate meridional S 4 N 4 2− ligand coordinating via two sulphurs and one nitrogen atom.

Investigations into the reaction of S4N4with [PPh4]2[Pd2Cl6]. The X-ray crystal structures of [PPh4]2[Pd2(μ-S2N2)Cl6] and [PPh4]2[Pd2(μ-S2N2)Cl4]

Abstract S4N4 reacts with [PPh4]2[Pd2Cl6] (1) in CH2Cl2 to give a mixture of [PPh4]2[Pd2(μ-S2N2)Cl6] (2) and [PPh4]2[Pd2(μ-S3N2)Cl4] (3). X-ray crystallography reveals (2) to contain neutral S2N2 as a bridging ligand whilst (3) constitutes only the second example of a complex of the bridging S3N22− ligand.

The first metal complexes containing tellurium-sulphur-nitrogen anions ; X-ray structure of [Pt(TeSN2H)(PMe2Ph)2[]BF4]

Reaction of Te 3 N 2 SCl 2 with cis-PtCl 2 (PMe 2 Ph) 2 and 1,8-diazabicyclo[5.4.0]undec-7-ene provides the first route to a metal-tellurium-sulphur-nitrogen complex, Pt(TeSN 2 )(PMe 2 Ph) 2 (1), the only example of a complex containing the TeSN 2 2− ligand. Complex 1 reacts with a dilute solution of HBF 4 •Et 2 O to give [Pt(TeSN 2 H)(PMe 2 Ph) 2 ][BF 4 ] (2), the X-ray structure of which reveals the first example of a M-Te-S-N ring.

The preparation and X-ray structure of (disulphurdinitrido)bis(triphenylphosphine) platinum(II)—tetrachloroform solvate, Pt(S2N2)(PPh3)2·4CHCl3

Abstract Reaction of Pt(PPh3)3 with S4N4H4 gives cis-Pt(S2N2)(PPh3)2 (1) in 45% yield. 1 was characterised be IR

The preparation, X-ray crystal structure and theoretical study of [CoCp2][S3N3], (Cp = cyclopentadienyl), a novel stacking compound incorporating multiple C–H ⋯ N(pπ) interactions

Reaction of cobaltocene, [CoCp2], with S4N4 in tetrahydrofuran (thf) results in precipitation of the cobaltocenium salt [CoCp2][S3N3]1 in good yield; the X-ray crystal structure together with theoretical calculations reveal an accumulation of unique C–H ⋯ N ⋯ H–C (pπ) interactions that result in the formation of continuous stacks of alternating cations and anions.

The preparation and use of disulphurdinitrido complexes: The X-ray structure of [PPh4][S3N3]

Abstract The preparation of M(S2N2)(PR3)2 (M = Pd or Pt) (1) complexes by reaction of MCl2(PR3)2 with S4N4H4 in the presence of diazabicycloundecane is described. A variety of other reagents also give rise to 1; in particular S4N4-BuLi. The reactive intermediate in the latter case appears to be S3N3− which has been characterized by X-ray crystallography as the PPh4+ salt: tetragonal, space group P 4 , a = 17.579(5), c = 7.447(2) A. The protonation of 1 to [M(S2N2H)(PR3)2]X (X = Cl− or BF4−) and the use of 1 in the preparation of S3N2O is reported.

The preparation and X-ray crystal structure of [Co(Ph2SNH)6]Cl2, a homoleptic sulfimide complex exhibiting cooperative, directed hydrogen bonds between cations and anions

Abstract At ambient temperatures, in CH3CN, a six-fold excess of S,S-diphenylsulfimide (1) reacts with anhydrous CoCl2 to give [Co(Ph2SNH)6]Cl2 (2), the first example of a homoleptic sulfimide complex. In addition to the expected octahedral coordination geometry, X-ray crystallography reveals significant directed hydrogen bonding from the NH groups on the ligands to the chlorides. Thus the three NH bonds on opposite coordination faces act as cooperative hydrogen-bonding pockets for the chloride counterions.