This perspective evaluates the results of recent investigations of binary chalcogen–nitrogen mole... more This perspective evaluates the results of recent investigations of binary chalcogen–nitrogen molecules, especially nitrogen-rich systems, with a focus of new structures, bonding insights and applications.
The reactions of (Me3SiNR)PPh2 (NSiMe3) (R=H, SiMe3) with (NSCl)3 or SxCl2 (x=1, 2) provide impro... more The reactions of (Me3SiNR)PPh2 (NSiMe3) (R=H, SiMe3) with (NSCl)3 or SxCl2 (x=1, 2) provide improved preparative routes to mixed phosphazene-thia-zene ring systems, e.g. (Ph2PN) (SN)2, 1,3- and 1,5-(Ph2PN)2(SN)2. The interaction of these heterocycles with protonic and Lewis acids, e.g. HBF4, BCl3, MeSO3CF3, has been investigated in order to determine the site of attack and the effect of adduct formation on
Reaction of potassium carbonate with elemental sulfur or selenium in acetone in the presence of [... more Reaction of potassium carbonate with elemental sulfur or selenium in acetone in the presence of [PPN]Cl (PPN = (Ph3P)2N) produces catena-[S12]2−, the longest structurally characterised polysulfide dianion, or spiro-[Se11]2− as ion-separated [PPN]+ salts.
Correction for ‘The role of polysulfide dianions and radical anions in the chemical, physical and... more Correction for ‘The role of polysulfide dianions and radical anions in the chemical, physical and biological sciences, including sulfur-based batteries’ by Ralf Steudel et al., Chem. Soc. Rev., 2019, 48, 3279–3319.
Polysulfide dianions and radical anions play a crucial role in biological chemistry, geochemical ... more Polysulfide dianions and radical anions play a crucial role in biological chemistry, geochemical processes, alkali metal–sulfur batteries, organic syntheses, coordination chemistry, and materials sciences.
Selenium and tellurium form binary halides in which the chalcogen can be in formal oxidation stat... more Selenium and tellurium form binary halides in which the chalcogen can be in formal oxidation states (IV), (II) or (I). They are versatile reagents for the preparation of a wide range of inorganic and organic selenium and tellurium compounds taking advantage of the reactivity of the chalcogen–halogen bond. With the exception of the tetrafluorides, the tetrahalides are either commercially available or readily prepared. On the other hand, the low-valent species, EX2 (E = Se, Te; X = Cl, Br) and E2X2 (E = Se, Te; X = Cl, Br) are unstable with respect to disproportionation and must be used as in situ reagents. Organoselenium and tellurium halides are well-known in oxidation states (IV) and (II), as exemplified by REX3, R2EX2 and REX (R = alkyl, aryl; E = Se, Te; X = F, Cl, Br, I); mixed-valent (IV/II) compounds of the type RTeX2TeR are also known. This chapter surveys the availability and/or preparative methods for these widely used reagents followed by examples of their applications in ...
The reactivity of the chalcogen–nitrogen bond toward main-group element or transition-metal halid... more The reactivity of the chalcogen–nitrogen bond toward main-group element or transition-metal halides, as well as electrophilic and nucleophilic reagents, is the source of a variety of applications of Se–N and Te–N compounds in both inorganic or organic chemistry. The thermal lability of Se–N compounds also engenders useful transformations including the formation of radicals via homolytic Se–N bond cleavage. These aspects of Se–N and Te–N chemistry will be illustrated with examples from the reactions of the binary selenium nitride Se4N4, selenium–nitrogen halides [N(SeCln)2]+ (n = 1, 2), the synthons E(NSO)2 (E = Se, Te), chalcogen–nitrogen–silicon reagents, chalcogen(IV) diimides RN=E=NR, the triimidotellurite dianion [Te(NtBu)3]2−, chalcogen(II) amides and diamides E(NR2)2 (E = Se, Te; R = alkyl, SiMe3), and heterocyclic systems.
Dalton transactions (Cambridge, England : 2003), Jan 31, 2018
The chemistry of the chalcogen-centred methanides [HC(PRE)] (E = S, Se, Te; R = alkyl, aryl) (PC(... more The chemistry of the chalcogen-centred methanides [HC(PRE)] (E = S, Se, Te; R = alkyl, aryl) (PC(H)P-bridged anions) is less well-developed than that of the isoelectronic imidodiphosphinates [N(PRE)], which are PNP-bridged analogues. The objective of this Perspective is to compare the chemistry of s-block metal complexes of the PC(H)P- and PNP-bridged anions in the context of synthetic approaches, X-ray (solid-state) structures, multinuclear NMR spectra, redox behaviour, and applications in coordination and inorganic heterocyclic chemistry. The related monochalcogeno-centred anions [HC(PR)(PRE)] and [N(PR)(PRE)] (E = S, Se, Te; R = alkyl, aryl) are also included in the discussion. Consideration of the similarities and, especially, the differences in the properties and reactions of the methanides with those of their imidodiphosphinate analogues reveals a number of areas in which the significance of the PC(H)P-bridged anions could be advanced.
The cyclocondensation reaction of primary amines with pnictogen and chalcogen halides is a major ... more The cyclocondensation reaction of primary amines with pnictogen and chalcogen halides is a major preparative route for the generation of inorganic heterocycles involving a Group 15 or 16 element linked to nitrogen.
The fundamental chemistry and significance of S,N and S,N,O anions and their conjugate acids in a... more The fundamental chemistry and significance of S,N and S,N,O anions and their conjugate acids in a variety of settings are discussed.
This perspective evaluates the results of recent investigations of binary chalcogen–nitrogen mole... more This perspective evaluates the results of recent investigations of binary chalcogen–nitrogen molecules, especially nitrogen-rich systems, with a focus of new structures, bonding insights and applications.
The reactions of (Me3SiNR)PPh2 (NSiMe3) (R=H, SiMe3) with (NSCl)3 or SxCl2 (x=1, 2) provide impro... more The reactions of (Me3SiNR)PPh2 (NSiMe3) (R=H, SiMe3) with (NSCl)3 or SxCl2 (x=1, 2) provide improved preparative routes to mixed phosphazene-thia-zene ring systems, e.g. (Ph2PN) (SN)2, 1,3- and 1,5-(Ph2PN)2(SN)2. The interaction of these heterocycles with protonic and Lewis acids, e.g. HBF4, BCl3, MeSO3CF3, has been investigated in order to determine the site of attack and the effect of adduct formation on
Reaction of potassium carbonate with elemental sulfur or selenium in acetone in the presence of [... more Reaction of potassium carbonate with elemental sulfur or selenium in acetone in the presence of [PPN]Cl (PPN = (Ph3P)2N) produces catena-[S12]2−, the longest structurally characterised polysulfide dianion, or spiro-[Se11]2− as ion-separated [PPN]+ salts.
Correction for ‘The role of polysulfide dianions and radical anions in the chemical, physical and... more Correction for ‘The role of polysulfide dianions and radical anions in the chemical, physical and biological sciences, including sulfur-based batteries’ by Ralf Steudel et al., Chem. Soc. Rev., 2019, 48, 3279–3319.
Polysulfide dianions and radical anions play a crucial role in biological chemistry, geochemical ... more Polysulfide dianions and radical anions play a crucial role in biological chemistry, geochemical processes, alkali metal–sulfur batteries, organic syntheses, coordination chemistry, and materials sciences.
Selenium and tellurium form binary halides in which the chalcogen can be in formal oxidation stat... more Selenium and tellurium form binary halides in which the chalcogen can be in formal oxidation states (IV), (II) or (I). They are versatile reagents for the preparation of a wide range of inorganic and organic selenium and tellurium compounds taking advantage of the reactivity of the chalcogen–halogen bond. With the exception of the tetrafluorides, the tetrahalides are either commercially available or readily prepared. On the other hand, the low-valent species, EX2 (E = Se, Te; X = Cl, Br) and E2X2 (E = Se, Te; X = Cl, Br) are unstable with respect to disproportionation and must be used as in situ reagents. Organoselenium and tellurium halides are well-known in oxidation states (IV) and (II), as exemplified by REX3, R2EX2 and REX (R = alkyl, aryl; E = Se, Te; X = F, Cl, Br, I); mixed-valent (IV/II) compounds of the type RTeX2TeR are also known. This chapter surveys the availability and/or preparative methods for these widely used reagents followed by examples of their applications in ...
The reactivity of the chalcogen–nitrogen bond toward main-group element or transition-metal halid... more The reactivity of the chalcogen–nitrogen bond toward main-group element or transition-metal halides, as well as electrophilic and nucleophilic reagents, is the source of a variety of applications of Se–N and Te–N compounds in both inorganic or organic chemistry. The thermal lability of Se–N compounds also engenders useful transformations including the formation of radicals via homolytic Se–N bond cleavage. These aspects of Se–N and Te–N chemistry will be illustrated with examples from the reactions of the binary selenium nitride Se4N4, selenium–nitrogen halides [N(SeCln)2]+ (n = 1, 2), the synthons E(NSO)2 (E = Se, Te), chalcogen–nitrogen–silicon reagents, chalcogen(IV) diimides RN=E=NR, the triimidotellurite dianion [Te(NtBu)3]2−, chalcogen(II) amides and diamides E(NR2)2 (E = Se, Te; R = alkyl, SiMe3), and heterocyclic systems.
Dalton transactions (Cambridge, England : 2003), Jan 31, 2018
The chemistry of the chalcogen-centred methanides [HC(PRE)] (E = S, Se, Te; R = alkyl, aryl) (PC(... more The chemistry of the chalcogen-centred methanides [HC(PRE)] (E = S, Se, Te; R = alkyl, aryl) (PC(H)P-bridged anions) is less well-developed than that of the isoelectronic imidodiphosphinates [N(PRE)], which are PNP-bridged analogues. The objective of this Perspective is to compare the chemistry of s-block metal complexes of the PC(H)P- and PNP-bridged anions in the context of synthetic approaches, X-ray (solid-state) structures, multinuclear NMR spectra, redox behaviour, and applications in coordination and inorganic heterocyclic chemistry. The related monochalcogeno-centred anions [HC(PR)(PRE)] and [N(PR)(PRE)] (E = S, Se, Te; R = alkyl, aryl) are also included in the discussion. Consideration of the similarities and, especially, the differences in the properties and reactions of the methanides with those of their imidodiphosphinate analogues reveals a number of areas in which the significance of the PC(H)P-bridged anions could be advanced.
The cyclocondensation reaction of primary amines with pnictogen and chalcogen halides is a major ... more The cyclocondensation reaction of primary amines with pnictogen and chalcogen halides is a major preparative route for the generation of inorganic heterocycles involving a Group 15 or 16 element linked to nitrogen.
The fundamental chemistry and significance of S,N and S,N,O anions and their conjugate acids in a... more The fundamental chemistry and significance of S,N and S,N,O anions and their conjugate acids in a variety of settings are discussed.
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