Residual traces of the metals copper and lead on an individual's skin may be elucidated by reaction of rubeanic acid with a gelatine lift taken from the target area in question, yielding intensely coloured reaction products. This non-invasive technique has been shown to offer promise in chemically mapping the distribution of the minute metal residues across an individual's hand deposited through touching metal items, a technique with potential forensic significance.

Faded, or actively removed text on thermally printed paper samples may be enhanced and retrieved through the use of a simple iodine fuming procedure. The recovery of printed documentation evidence in this fashion is neither affected by prior fingerprint enhancement techniques (such as ninhydrin or DFO), nor by sample age. This method allows, for the first time, evidence to be obtained from completely faded thermal paper samples (receipts, for example) as well as allowing deliberately removed printed text (a consequence of solvent washing pre-treatment in latent fingerprint enhancement procedures) to be recovered.

Polymerisation of S2N2 to (SN)x on metallic surfaces is induced by interaction with the minute corrosion signatures of removed (by washing) fingerprints; as vapour-phase S2N2 is employed, it follows that the process has the potential to rapidly screen large/convoluted metal pieces, such as explosive device fragments whose prints were wiped by the detonation.

Exposure of fingerprints to S2N2 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 S2N2 with traces of inkjet inks, for example the minute amounts left by the contact between printed paper and an envelope.

Reaction of the mixed thioether/ether crowns [9]aneO2S 1, [12]aneO3S 2 and [18]aneO4S23 with one mol. equivalent of the aminating agent MSH (o-mesitylsulfonylhydroxylamine) in Et2O results in the formation of the mono-sulfimidated systems {[9]aneO2(SNH2)}+1a, {[12]aneO3(SNH2)}+2a and {[18]aneO4S(SNH2)}+3a, while using two mol. equivalents of MSH with 3 gives the disulfimidium cation {[18]aneO4(SNH2)2}2+3b. All of these species have been isolated in good yields as the [mesSO3]− (mes = 2,4,6-Me3C6H2) salts and can be readily converted to the [BPh4]− salts by metathesis with Na[BPh4]. Treatment of 1a or 2a with lithium diisopropylamide (LDA) and N-bromosuccinimide (NBS) at −78 °C, followed by addition of a further equivalent of the parent thia/oxa crown, gives monocationic N-bridged sulfimide bicyclic compounds (4 and 5 respectively), in which the crowns are linked by the sulfimidic nitrogen. Reaction of 3a with LDA and NBS leads to formation of the {([18]aneO4S2)N}+ cation 6 which exhibits an intramolecular S–N–S bridge. Crystallographic studies on representative examples of each compound type are described, together with their spectroscopic properties.

Reaction of o-mesitylsulfonylhydroxylamine (MSH) with Ph2Se results in the [Ph2SeNH2]+ cation; low temperature deprotonation (LDA), bromination (NBS) and then treatment with Ph2Se–Na[BPh4] generates [Ph2SeNSePh2][BPh4], via the selenimides Ph2SeNH and Ph2SeNBr.

Reaction of S2N2 vapour with Na-ZSM-5 results in rapid polymerisation and inclusion of the resulting (SN)x within the zeolite channels.

Reaction of [Bu4N]2[Pd2Br6(Se2N2)] with [14]aneS4 results in eventual formation of Se4N4; intermediates in this reaction include an air-sensitive insoluble material which reacts with [PtCl2(PMe2Ph)]2 to give the first example of a platinum adduct of Se2N2 and with [Pd2Br6]2− to regenerate the starting material.

Reaction of [18]aneO5S with the aminating agent MSH results in the {[18]aneO5SNH2}+ cation which may be converted through to the linked crown system [({[18]aneO5S}2N)]+via deprotonation, bromination and reaction with the parent crown; significantly, despite their positive charge, both systems can coordinate sodium cations to the ether linkages.

Reaction of copper(II) terephthalate and S,S′-diphenylsulfimide in MeOH gives a 1-D coordination polymer with inner-sphere terephthalate ligands; addition of H2O to the reaction solution, however, results in a hydrogen bonded array with the terephthalate anion acting as an outer-sphere ligand.

The N-bromosulfimide Ph2SNBr reacts with a range of selenium sources including, uniquely, elemental selenium itself, to generate the explosive nitride Se4N4.

The complex [Cu(Ph2SNH)4][PF6]2 crystallises in three different forms, two of these are true polymorphs whilst the third form is a pseudo-polymorph as solvent molecules are incorporated into the lattice. The forms differ in both the geometry of the copper centre and the orientation and form of the supramolecular interactions observed.

Preparation and protonation of the hydroxy derivatised sulfimides 2- and (4-C6H4OH)(Ph)SNH gives a sulfimidium cation with three hydrogen bond donors, two NH hydrogens and an OH hydrogen. These all interact with the chloride counterion to give extended hydrogen bonded arrays. The effect of the position of the hydroxy group on the network produced is investigated. Also reported is the structure of the bis-sulfimidium salt [1,3-(PhSNH2)2C6H4]Cl2 which also exhibits a hydrogen bonded array.

Reaction of a solution of CuSO4 and S,S′-diphenylsulfimide, Ph2SNH 1, with sodium salts of trimesic acid (H3tma) in MeOH gives the 2-D coordination network [Cu3(Ph2SNH)6(tma)2] in which each trimesate is bound to three copper centres. Addition of other solvents to the reaction mixture causes a change in the shape of the network. By this route, three forms have been prepared and characterised by X-ray crystallography. These include the known honeycomb, 2, and brick-wall, 3, motifs and a herringbone, 4, arrangement which is novel for transition metal-containing trimesate complexes. Key to the supramolecular isomerism observed is the ability of 1 to facilitate structural isomerism at copper(II) centres. In contrast to 2 in which the copper centres are square planar, 4 is analogous to an inter-allogon, with both planar and tetrahedral copper centres. Also prepared is a related complex 5 which is composed of discrete units of three copper centres. These are further linked into a 2-D network by hydrogen bonds.

The brominated sulfimide Ph2SNBr reacts with diphosphines 1,2-(PPh2)2C2H4 and 1,4-(Ph2P)2(C6H4) to give the bis-N-phosphoniosulfimidium cations [1,2-(Ph2PNSPh2)2C2H4]2+ and [1,4-(Ph2PNSPh2)2(C6H4)]2+, respectively. Treatment of the bis-sulfimide 1,4-[PhSNH]2C6H4 with N-bromosuccinimide results in 1,4-[PhSNBr]2C6H4, which in turn reacts with triphenylphosphine to generate [1,4-(PhS{NSPPh3})2C6H4]Br2. Both Ph2SNBr and 1,4-[PhSNBr]2C6H4 react with the thio-ether crown [9-ane]S3, giving [9[ane]S3NSPh2]Br and [1,4-{[9-ane]S2S(NSPh)2C6H4]Br2, respectively. The first examples of seleniosulfimidium salts have been isolated from the reactions of Ph2SNBr and 1,4(PhS{NBr})2C6H4 with Ph2Se and the structures of the [Ph2SNSePh2]+ and [1,4-(PhSNSePh2)2C6H4]2+ cations confirmed by X-ray crystallography. Reaction of 1,2-PhS(NH)C6H4SPh with one equivalent of N-bromosuccinimide followed by addition of Na[BPh4] results in [1,2-(PhS)2(μ-N)C6H4][BPh4] in which a CCSNS ring is observed; two forms of this material may be isolated upon crystallisation—X-ray crystallography reveals them to differ by the relative orientations of the phenyl rings.

S,S′-diphenylsulfimide Ph2SNH (1) reacts with copper tetrafluoroborate to give a number of different products including two concomitant polymorphs of [Cu(Ph2SNH)4][BF4]2, the interallogon [Cu(Ph2SNH)4]2[BF4]4 and [Cu(Ph2SNH)4][Cu(Ph2SNH)5][BF4]4, an extremely rare example of a homoleptic system exhibiting four- and five-coordinate metal centres in the same unit cell.

Protonation of Ph2SNH 1 with HCl gives [Ph2SNH2]Cl 2 which shows strong hydrogen bonding between the sulfimidium NH2 unit and the chloride anion resulting in a zig-zagged 1-D structure in which stacks of [Ph2SNH2]+ cations are observed. The analogous bromide, [Ph2SNH2]Br, 3 is not isostructural and shows an extended structure with two stacks of cations linked by bridging bromide anions. Reaction of two equivalents of 2 with CuCl2 gives [Ph2SNH2]2[CuCl4] 4 in two forms. One of these, 4a, which is formed at ambient temperature, is orange and contains distorted tetrahedral [CuCl4]2− anions whilst the lower temperature form, 4b, is green and contains both distorted tetrahedral and square planar copper geometries in the same unit-cell. Both structures show extended arrays formed via the hydrogen bonding between the sulfimidium NH2 unit and chlorides.

Treatment of 1,4-(PhS)2C6H4 and 1,2-(PhS)2C6H4 with the appropriate amount of O-mesitylsulfonylhydroxylamine (MSH) yields the corresponding protonated sulfimides, both of which may be deprotonated with DBU to give the hydrated free sulfimides 1,4-(PhS{NH})2C6H4·2H2O 1a and 1-(PhS{NH})-2-(PhS)C6H4·H2O 2a. The X-ray crystal structures of both 1a and 2a, together with that of the well-known sulfimide Ph2SNH·H2O 3a, all reveal extended hydrogen-bonded arrays involving the N–H units and the waters of crystallisation. Crystals of 1b, the dehydrated form of 1a, also readily form, while removal of the water from 3ain vacuo followed by slow evaporation of a solution in diethyl ether under anaerobic conditions leads to crystals of Ph2SNH 3b; the X-ray crystal structures of both 1b and 3b also reveal extended arrays formed from N–H⋯N interactions. In contrast, dehydration of 2a breaks down the extended structure resulting in the formation of an oil.

Green crystalline [Cu(Ph2SNH)4][CuBr2(Ph2SNH)2]Br2 (2) forms when the product of the reaction of CuBr2 with Ph2SNH (1) (molar ratio 1:3) in MeCN is extracted into CH2Cl2–60/80 petroleum ether and the solvents allowed to evaporate slowly. The product is notable for two reasons: not only does it contain the CuBr2(Ph2SNH)2 unit in the hitherto unseen planar isomer (the free material forming only the pseudo-tetrahedral isomer), but, more significantly, it is also the first example of a structurally characterised [CuL4][CuX2L2]X2 system.

Reaction of excess Ph2SNH (1) with [PPh4]2[Pd2Br6] results in the formation of homoleptic [Pd(Ph2SNH)4]Br2. In contrast the analogous reaction of the N-substituted sulfimide Ph2SNCH2CH2CN (2) with [PPh4]2[Pd2Br6] only results in the formation of trans-[PdBr2(Ph2SNCH2CH2CN)2] (3) even if the ligand is present in large excess. Lowering the reaction ratio to 2:1 (ligand: dimer) allows isolation of [PPh4][PdBr3(Ph2SNCH2CH2CN)] (4). Compounds 3 and 4 constitute the first examples of fully characterised complexes of N-substituted sulfimides and X-ray crystallography confirm the ligands to be bound to the metal through nitrogen; although the nitrile end groups of the substituents have the potential to bind to metals, no evidence for this is seen in these particular systems.

Polymerisation of S2N2 to (SN)x on metallic surfaces is induced by interaction with the minute corrosion signatures of removed (by washing) fingerprints; as vapour-phase S2N2 is employed, it follows that the process has the potential to rapidly screen large/convoluted metal pieces, such as explosive device fragments whose prints were wiped by the detonation.

Imino(triphenyl)phosphorane, Ph3PNH (1), reacts with nitrile complexes of Pt(IV) to generate hydrolytically sensitive [PtCl4{NHC(R)NPPh3}2] (R = Me 2a, Et 2b, Ph 2c), and with the Pt(II) complex [PtCl2(EtCN)2] to give [PtCl2(EtCN){NHC(Et)NPPh3}] (3) and [PtCl2{NHC(Et)NPPh3}2] (4); X-ray crystallography performed upon (2b) and (3) confirms the presence of an imine/nitrile addition ligand bound by the terminal nitrogen.

Reaction of [18]aneO5S with the aminating agent MSH results in the {[18]aneO5SNH2}+ cation which may be converted through to the linked crown system [({[18]aneO5S}2N)]+via deprotonation, bromination and reaction with the parent crown; significantly, despite their positive charge, both systems can coordinate sodium cations to the ether linkages.

Reaction of [Bu4N]2[Pd2Br6(Se2N2)] with [14]aneS4 results in eventual formation of Se4N4; intermediates in this reaction include an air-sensitive insoluble material which reacts with [PtCl2(PMe2Ph)]2 to give the first example of a platinum adduct of Se2N2 and with [Pd2Br6]2− to regenerate the starting material.

Exposure of fingerprints to S2N2 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 S2N2 with traces of inkjet inks, for example the minute amounts left by the contact between printed paper and an envelope.

Reaction of S2N2 vapour with Na-ZSM-5 results in rapid polymerisation and inclusion of the resulting (SN)x within the zeolite channels.

Reaction of o-mesitylsulfonylhydroxylamine (MSH) with Ph2Se results in the [Ph2SeNH2]+ cation; low temperature deprotonation (LDA), bromination (NBS) and then treatment with Ph2Se–Na[BPh4] generates [Ph2SeNSePh2][BPh4], via the selenimides Ph2SeNH and Ph2SeNBr.

Reaction of the mixed thioether/ether crowns [9]aneO2S 1, [12]aneO3S 2 and [18]aneO4S23 with one mol. equivalent of the aminating agent MSH (o-mesitylsulfonylhydroxylamine) in Et2O results in the formation of the mono-sulfimidated systems {[9]aneO2(SNH2)}+1a, {[12]aneO3(SNH2)}+2a and {[18]aneO4S(SNH2)}+3a, while using two mol. equivalents of MSH with 3 gives the disulfimidium cation {[18]aneO4(SNH2)2}2+3b. All of these species have been isolated in good yields as the [mesSO3]− (mes = 2,4,6-Me3C6H2) salts and can be readily converted to the [BPh4]− salts by metathesis with Na[BPh4]. Treatment of 1a or 2a with lithium diisopropylamide (LDA) and N-bromosuccinimide (NBS) at −78 °C, followed by addition of a further equivalent of the parent thia/oxa crown, gives monocationic N-bridged sulfimide bicyclic compounds (4 and 5 respectively), in which the crowns are linked by the sulfimidic nitrogen. Reaction of 3a with LDA and NBS leads to formation of the {([18]aneO4S2)N}+ cation 6 which exhibits an intramolecular S–N–S bridge. Crystallographic studies on representative examples of each compound type are described, together with their spectroscopic properties.