7 oxygen, sulfur, selenium and tellurium

7 Oxygen, sulfur, selenium and tellurium

Pravat BhattacharyyaDOI: 10.1039/b408130g

A review of the literature during 2004 concerning the chemistry of the

Group 16 elements is presented. This review will attempt to clarify literature

highlights into distinct research themes within inorganic chemistry, and as in

previous years, an emphasis is placed on molecular species with novel

structures or unusual reactivity. Important aspects reported during 2004

include the capacity of the naked chalcogenide anions to support discretepolymetallic clusters and the isolation of unique examples of simple

chalcogen-containing species.

1 Sulfur, selenium and tellurium

The interaction of Group 16 donors with dihalogen species received further attention

in 2004. The first pseudohalogen adduct of a selenocarbonyl, generated from 1,3-

dimethyl-4-imidazoline-2-selone and cyanogen iodide, was prepared,1 the selenium–

iodine separation [3.300(1) A] in conjunction with DFT calculations suggesting

that the selenium atom is in a partial hypervalent state. Diiodine adducts of 1,4-

dimethylperhydro-1,4-diazepine-2,3-dithione and (SPPh2)2NH react with elemental

mercury at room temperature to give neutral square planar Hg(II) complexes with

S2I2 donor sets,2,3 while the sulfur atoms of Group 8 bis(dithiolene) complexes can

act as donors to diiodine,4 comparisons between experimental and calculated n(S–I)

frequencies permit an evaluation of their strength. Two adducts of formula

C48H32Br10Se8 are available upon bromination of selenanthrene,5 one product contains

a linear Br4 unit connecting selenium centres in adjacent molecules (4c–6e bond)

whereas the other possesses a linear Se2Br5 (7c–10e bond) unit. Lang and co-workers

report that dimesityl ditelluride is oxidised by diiodine to give Mes(I)Te(TeMes2), the

first aryltellurium(II) halide complex stabilised by a Te–Te bond from a telluroether.6

The mechanism of its formation involves disproportionation of the intermediate

MesTeI to Mes(I)Te(TeMes2), MesTeI3 and elemental tellurium. The interaction of

4,5-bis(bromomethyl)-1,3-dithiole-2-thione with iodine(I) monohalides generates

adducts exclusively through the thione centre (S…I 2.534–2.597 A), with the endocyclic

sulfur atoms being uninvolved in S…halogen interactions.7

Crystallographic and computational studies of organoselenides (2-YC6H4)SeX

(Y = N or O donor, X = halogen or pseudohalogen) reveal the importance of

Department of Chemistry, UMIST, P. O. Box 88, Manchester, UK M60 1QD

REVIEW www.rsc.org/annrepa | Annual Reports A

Annu. Rep. Prog. Chem., Sect. A, 2005, 101, 117–127 | 117

This journal is � The Royal Society of Chemistry 2005

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http://dx.doi.org/10.1039/b408130g

http://pubs.rsc.org/en/journals/journal/IC

http://pubs.rsc.org/en/journals/journal/IC?issueid=IC005101

non-bonded intramolecular YASe interactions in stabilising these low-valent

compounds.8–10 Poleschner and Seppelt have generated ArSeF by fluorination of

Ar2Se2 or ArSeSiMe3 with xenon difluoride and used low-temperature 77Se/19F

NMR for characterisation.11 Klapotke et al. isolated the first stable covalent

selenium azide, (2-Me2NC6H4)SeN3, in near-quantitative yield by metathesis from

the chloride using AgN3 or NaN3,12 as well as pseudohalogen derivatives of

tellurium, notably Te(CN)x (x = 2 or 4) and Ph5TeN3.13,14 The crystal structure

of Te(CN)2 is the first determination for a chalcogen cyanide. Binary azides of

selenium, tellurium and the heavier Group 15 elements were also studied by Knapp

and Passmore.15 C6F5SeCl and C6F5SeLi are versatile precursors to new

pentafluorophenylselenium(II) compounds;16 the chloride reacts with nitrogen

nucleophiles or silylated chalcogen species to give compounds with Se–S, Se–N

and Se–Se bonds, while Group 14 derivatives C6F5SeMMe3 (M = Si, Ge, Sn or Pb)

are produced from C6F5SeLi and Me3MHal.

The selenium(II) dialkanethiolates Se(SR)2 (R = Me or tBu) undergo exchange

of substituents with Se(II) and Te(II) dithiolates, and also with thiols if a catalytic

amount of p-toluenesulfonic acid is present.17 Similarly, mixing dilute methanolic

solutions of dimethyl trisulfide and diorganodiselenides at room temperature

generates trichalcogenides containing either –SeS2–, –SSeS–, –Se2S–, –SeSSe– or

–Se3– linkages via chalcogenide exchange.18 Branched isomers –Se–Se(LSe)– were

also detected. In related work, the second example of a structurally characterised

diorganotriselenide was reported.10 Munchow and Steudel have synthesised sulfur-

rich acyclic thiaalkanes by treatment of the titanocene thiolates [Cp2Ti(SSR9SS)]

(R9 = CMe2 or 1,1-C6H10) with Ph3CSCl, affording [Cp2TiCl(SSR9S3CPh3)], and

quenching with electrophiles such as RSCl, SO2Cl2 or SxCl2.19 The thiaalkanes are

stable for several weeks at 4 uC but undergo decomposition at higher temperatures.

Oxidative coupling of phosphonodithioates [Fc(RO)PS2]2 and [An(RO)PS2]2 using

KI/I2 gives dithiophosphonodisulfides [P(S)–S–S–P(S) linkage], several of which

were investigated crystallographically.20

Disulfur monoxide, SLSLO, generated by the retro-Diels–Alder reaction of a

sulfur-rich cycloadduct, rapidly disproportionates to S3 and SO2.21 In a separate

study the decomposition of S2O to SO2, S3, S4 and S5O, a process cited as relevant

for understanding the chemistry occurring on Jupiter’s moon Io, was probed by gas-

phase ab initio calculations at the G3X(MP2) level.22 The rotational spectrum of

thiozone, S3, obtained using high-resolution molecular beam FT microwave spectro-

scopy, discloses important structural data for the molecule [d(SLS) 1.917(1) A, S–S–S

117.36(6)u].23 During the reaction of the thioketene S-oxide tBu2CLSLO with

Lawesson’s Reagent, sulfur atom transfer from the phosphorus compound affords a

thiirane-2-thione in high yield at room temperature.24 The cis-thiolate groups of a

nickel(II) complex with a macrocyclic N2S2 ligand bind two sulfur dioxide molecules

to give an adduct which is stable in vacuo for 12 h without SO2 loss, although

displacement occurs if a solution of the complex is purged with an inert gas.25

Exposure of the adduct to dioxygen oxidises the bound SO2 molecules to [SO4]22.

118 | Annu. Rep. Prog. Chem., Sect. A, 2005, 101, 117–127


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Under ambient conditions tellurium tetrahalides react with triphenylphosphine

in thf to give [{(Ph3PO)2H}2][Te2X10] (X = Cl, Br) and [(Ph3PO)3(OH3)]2[TeI6], while

from TeBr4 a formally zwitterionic species Ph3PO(CH2)4TeBr4 is also available,

derived by ring-opening of the solvent.26 Hexavalent organotellurium compounds

TeAr6 (Ar = Ph or 4-CF3C6H4) are formed in the reaction of TeCl4 with four

equivalents of ArLi in diethyl ether at 278 uC, pentaaryl halides TeAr5Hal (Hal = Cl

or Br) were prepared by halogenating Li[TeAr5] intermediates with sulfuryl chloride

or dibromine respectively.27

DFT studies of the ring currents in chalcogen-containing monocycles were used to

probe their aromaticity. Diatropic p-currents reinforced by s-circulations were

found in [S3N3]2, [S4N3]+, [S4N4]2+ and [S5N5]+, but the currents were in opposition

in the four-membered rings [S4]2+, [Se4]2+ and S2N2, compatible with height profiles

of calculated nucleus-independent chemical shifts.28 The electronic and molecular

structures of the square-planar 6p electron systems E2N2 and [E4]2+ (E = S, Se or Te)

were also analysed by Suontamo and Laitinen.29 The charge-density distribution of

the sulfur imides MeS(NtBu)(NHtBu), (tBuN)2(ButNH)SCH2S(NHtBu)(NtBu)2,

S(NtBu)2 and S(NtBu)3 were determined experimentally using high-resolution

X-ray diffraction at 100 K and found to agree closely with ab initio calculations.30

The authors concluded that in S(NtBu)2 and S(NtBu)3 the central planar SNx units

possess multicentre bonding whereas for the other molecules the sp3 hybridisation of

the nitrogen centres suggest that an S+–N2 designation is more accurate. Potassium

18-crown-6 salts of [RNSN]2 (R = Ad, tBu, SiMe3, Ph or 4-FC6H4) and [NSN]22

were synthesised by treatment of trimethylsilylated precursors with [K(18-crown-6)]-

[tBuO] and studied crystallographically.31 The bond lengths in the former suggest

a thiazylamide form [R–N–SMN]2, rather than an [R–NLSLN]2 (sulfur diimide)

structure. The salts are thermally stable and very soluble in aprotic organic solvents.

Thermal decomposition of Se(NAd)2 in thf affords inter alia a new five-membered

cyclic imide, Se3(NAd)2, a new ring size for a chalcogen imide (although the naked

[Se3N2]+ cation is also known).32 Other products of the decomposition assigned by77Se NMR include Se3(NAd)3 and two partially hydrolysed species, AdNSe(m-

NAd)2SeO and OSe(m-NAd)2SeO. Anhydrous salts of 1,2,3,4-thiatriazole-5-thiolate,

[CS2N3]2, were reported by Klapotke and Crawford, including crystallographic

analysis of the [NH4]+ and [NMe4]+ salts.33 Also described were improved syntheses

of the dipseudohalogen (CS2N3)2 and the interpseudohalogen CS2N3CN, and

calculations on the hypothetical [CSe2N3]2 and [CTe2N3]2 anions. New heterocyclic

1,3,2-dithiazolyl radicals were studied using variable temperature magnetic

susceptibility measurements, X-ray crystallography and EPR spectroscopy.34–36



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Novel cyclic and linear polychalcogenide species were synthesised by several

routes. Solvothermal methods afford [(AgI)2E6] (E = Se, Te), containing neutral E6

rings stabilised in an AgI matrix,37 [Se6]22 and [TeSe2]22 chains are generated from

reactions involving manganese(II) chloride, K2Se3 and either Se or Te at 433 K.38

Both [NEt4]2[Te3Se6] and [NEt4]2[Te3Se7] , which contain one-dimensional anionic

chains of Te3Se5 or Te3Se6 rings, respectively, linked by selenium atoms, were

prepared by reactions of [Ten]22 and [Sen]22 salts of ammonium cations in dmf at

293 K.39 One-dimensional polymeric chains of [Te6]2+ cations, comprising [Te5]2+

rings joined via single Te atoms, were generated by chemical vapour transport.40

Computational studies by Krossing and Passmore provide evidence for the

previously unknown 10p electron homocycle [S6]2+ in solutions of [S8](AsF6)2 in

sulfur dioxide and propose that p*–p* transitions in this dication are responsible for

the colour of solutions of S8 in strong protonic acids.41

The coordination chemistry of chalcogen donor ligands continue to attract

attention. Recent developments in the chemistry of metal–sulfoxide complexes

were reviewed by Alessio42 and Calligaris.43 Closely related to sulfoxides, sulfimides

display similar coordinative versatility. Reaction of Ph2SNH with copper(II) sulfate

and sodium salts of trimesic acid (H3tma) gives two-dimensional networks

[Cu3(Ph2SNH)6(tma)2] whose topologies (herring-bone, brick wall or honeycomb)

vary with recrystallisation solvent.44 [Cu(Ph2SNH)4][PF6]2 crystallises in three

different forms, two of which are polymorphic whereas the third is a pseudo-

polymorph, owing to solvent incorporation into the lattice.45 The product

distribution is primarily controlled by temperature, the forms differing in geometry

at the copper centre and the nature of the supramolecular interactions.

Cleavage of [FcP(S)(m-S)]2 with sodium ethoxide affords [FcP(OEt)S2]2, which

forms mononuclear complexes with Group 10 metals,46 while bis(phosphonodithio-

ates) [M{S2P(OR)2}2] (M = Zn or Cd, R = iPr or Cy) react with 4,49-bipyridyls

to give coordination polymers with linear, zigzag or arched topologies.47,48

Metal trithiophosphonates [(CyPS3)Li2?thf?tmen]2 and [(CyPS3)Mg?thf2]2 were

prepared by metallating CyPH2 with either n-butyllithium in thf–tmen or dibutyl-

magnesium respectively, followed by addition of sulfur;49 the molecules crystallise

as dimer pairs with the three sulfur atoms of the anion coordinated to the alkali

metal cations.

Pyrazine-2,3-diselenolate (pds22) reacts with PtCl2 to give platinum(IV) species

[Pt(pds)3]22 or [Pt2(pds)5]22, depending upon the molar ratio of reagents used (3:1

or 2:1, respectively), while pulse field gradient spin-echo NMR experiments reveal

the presence in solution of trimetallic species [{Pt(pds)3}{Pt(pds)2}2]22 derived

from addition of [Pt(pds)2] to [Pt2(pds)5]22.50 Pds22 stabilises a mixed-valence two-

dimensional coordination polymer CuI[CuIII(pds)2] in which the Cu(I) cations

are coordinated by the nitrogen and selenium atoms from adjacent complex

anions.51 Obtained unexpectedly during electrocrystallisation of Na[CuIII(pds)2],

CuI[CuIII(pds)2] is unique in its co-existence of Cu(I) and Cu(III) centres without

charge-transfer between them. Woollins and co-workers have investigated oxidative

addition reactions of dichalcogen derivatives of naphthalene, acenaphthene

and phenanthrene with Pt(0), Pt(II) and Ir(I) complexes,52,53 and an unusual

2-(arylmercapto)aryl mercaptan complex is isolable from the reaction of

[RuCl(Tp)(cod)] with Ph2S2 or (p-tolyl)2S2, the reaction pathway being dictated by

the bulk of the Tp ligand and the high affinity of the RuTp fragment for the strong

p-acceptor CO ligand.54



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The 1,5-diselenacyclooctane complexes [MCl3{[8]aneSe2}] (M = As, Sb or Bi)

exhibit ladder structures composed of planar M2Cl6 cores linked through the trans-

selenium atoms of the diselenoether ligands.55 Whereas the arsenic adduct has an

polymeric chain structure, the antimony compound is composed of discrete dimers.

Cyanodithioimidocarbonate, [C2N2S2]22, generates mononuclear S,S9-chelates with

Pt(II) and Pd(II), while for Rh(I) and Ir(I) dimeric complexes are formed in which

the sulfur atoms bridge two metal centres, producing cores with cubane-type

geometries.56 The monoanion of (tBuNH)3PLS forms four-membered N,S-chelates

at Rh(I) and Mo(VI) but for Ni(II) an asymmetrical bis-chelate is found with the

anion bound in hard (N,N9-) and soft (N,S-) modes.57 A new ambidentate indene

ligand with pendant thiophosphoryl and amine donors acts as an N,S-bidentate

donor at Rh(I) in its neutral form, but upon deprotonation the indenyl anion binds

to Rh(I) and Mn(I) centres in C,S-bidentate and g5-modes, respectively.58

Transition metal clusters with bridging chalcogenide anions remain prominent.

The undecanuclear complex [Cu11(m9-Se)(m3-Br)3{Se2P(OR)2}6] (R = Et, nPr or iPr)

contains a nonacoordinate selenide in a tricapped trigonal prismatic geometry,59

while [Zn4(m4-Se){Se2P(OR)2}6] is the first Zn4 tetrahedron stabilised by Se22.60

This cluster dissociates to monomeric and dimeric units in solution (VT 31P

NMR evidence), akin to the well-known dithiophosphate species, polymeric

and selenide-free forms of this cluster were also reported by the same authors.61

The orthoselenostannate anion, [SnSe4]42, reacts with divalent metals to give [M4(m4-

Se)(SnSe4)4]102 (M = Zn, Cd, Hg or Mn), whereas from mercury acetate

coordination polymers 3‘{[Hg4(m4-Se)(SnSe4)3]62} and 1

‘{[Hg(SnSe4)]22} are

available.62 Crystallographically characterised gold clusters constructed using

bis(trimethylsilyl)selenium include [Au5Se2(PPh3)4]Cl, [(Au3Se)2(dpph)3]Cl2 and

[Au10Se4(dpppe)4][InCl5], constructed by edge-sharing of Au3(m3-Se) tetrahedra.63

Binuclear aluminium b-diketiminate complexes [(dike)Al(m-E)2Al(dike)] (E = Se or

Te) and [(dike)Al(m-S3)2Al(dike)] have been structurally characterised. The m-Se/Te

species were prepared from reactions involving [Al(dike)H2] and elemental chalcogen

in the presence of catalytic amounts of tertiary phosphine,64 while for the polysulfide

the conformation of the Al2S6 ring differs from the octasulfur crown as the S3

chains are staggered rather than eclipsed.65 The first bimetallic telluroacyl complex,

[WFe(m-TeCTol)(CO)5Cp], was generated by reacting the alkylidene complex

[WFe(m-CTol)(CO)nCp] (n = 5 or 6) with elemental tellurium;66 by contrast,

m-telluride clusters were afforded when the bulkier 2,6-Me2C6H3 substituent was



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present in the alkylidene fragment. In [Ta4Se9I8], obtained from Ta/Se/I2 at 300 uC,

the tantalum atoms form a square, with four Se2 ligands bridging each Ta-Ta edge

and one m4-Se capping the Ta4 unit.67 Cyanide-terminated molybdenum clusters

[Mo6Se8(CN)6]62/72 and [Mo4Se4(CN)12]82 were prepared by treating Mo3nSe3n+2

cluster compounds (n = 2–‘) with cyanide salts,68 cuboidal heterobimetallic

cages [Mo3CuSe4]4+/5+ and [W3CuQ4]5+ (Q = S or Se) were generated by reacting

molybdenum and tungsten precursors with elemental copper,69 while [Ru9S8(p-

cymene)6]2+ and [Ru5S4(p-cymene)4]2+ were accessible from [Ru3S2(p-cymene)2-

(MeCN)3]2+ using Na2S?9H2O and NaSH respectively.70 The ruthenium clusters

were considered to be potential hydrodesulfurisation catalysts, since Ru–S phases are

more effective than Mo–Co–S systems.

Lithium–tin imido heterocubane clusters containing terminal SnLSe or SnLTe

bonds were prepared by chalcogenation of LiSn3N4 cages using elemental selenium

or tellurium respectively.71 The monomeric stannane–thione and –selone

[(Tbt)(Ditp)SnLX] (X = S or Se), which are kinetically stabilised by the sterically

demanding aromatic substituents, were prepared by dechalcogenating the tetra-

chalcogenastannolanes [(Tbt)(Ditp)Sn(E4)] with phosphines.72 The X-ray structure

of the stannaneselone reveals that d(SnLSe) = 2.373(3) A supporting the view that the

compound is structurally similar to a ketone, as is the case for the silicon and

germanium analogues, a result further borne out by 119Sn NMR spectra.

An array of polychalcogenate-containing anions are accessible by solid-state

synthetic methods. Heating B2S3 and BaS at 1000 uC for 24 h affords [Ba7(BS3)4S] in

which the Ba(II) centres have eight or nine sulfide donors whereas the thioborate

anions are not coordinated.73 Ternary alkali selenophosphates A[PSe6] (A = K,

Rb or Cs), available from A2Se/P2Se5/Se melts at 350 uC, contain one-dimensional

chains of [PSe2(Se4)]2, in which the PSe2 units are connected via linear [Se4]22

bridges.74 A simple new route to crystalline metal polysulfides utilising boron sulfides

was described.75 In a fused silica ampoule a tube containing metal oxide was placed

above another containing boron and sulfur powders. At temperatures exceeding

350 uC the boron sulfides formed in situ are sufficiently volatile to react in gaseous

form with the metal oxide. The generality of this procedure was demonstrated by the

synthesis of sixteen d- and f-block metal sulfides; the authors also speculated that

in situ formed boron selenides may behave in a similar capacity as a synthon for

metal selenides. A new three-dimensional antimony sulfide framework with one-

dimensional circular channels [Co(en)3][Sb12S19] was prepared solvothermally from

sulfur, en, cobalt(II) sulfide and antimony(III) sulfide at 170 uC.76

A kinetic study of the acid-dependent disproportionation of dithionate, [S2O6]22,

in the presence of dioxygen and a range of inorganic oxidants was conducted.77

These investigations confirmed that [S2O6]22 is not directly oxidised but undergoes

disproportionation and subsequent oxidation of the S(IV) species formed. Both



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Ce(III) and iodide ions catalyse this autoxidation process. Addition of thiocyanate to

an acidified aqueous solution of dichlorine rapidly generates an equilibrium mixture

of thiocyanogen, (SCN)2 and trithiocyanate, [SCN]32.78 The thiocyanogen subse-

quently decomposes to HSCN, H2SO4 and HCN, a process followed by stopped-

flow kinetics. The authors cite the relevance of these studies as delivering an insight

into the physiological role of enzymes which catalyse thiocyanate oxidation.

By using a very sterically bulky terphenyl substituent for stabilisation, an

Se-nitrososelenol (Bpq)SeNO was prepared by treatment of (Bpq)SeH with either

ethyl nitrite or S-nitrosoglutathione.79 Although sensitive to dioxygen, (Bpq)SeNO is

stable to water and is an important compound for developing our understanding of

NO-mediated modifications of selenoproteins. An unusual carbocation [CS2Br3]+

was isolated during the reaction of silver(I) salts with dibromine and carbon

disulfide; the crystal structure of the cation as the [Al{OC(CF3)3}4]2 salt reveals that

the cation is planar at carbon and the C–S lengths are intermediate between single

and double bond values.80

2 Oxygen

A new oxyanion of carbon, [OC(CO2)3]42, is found in the octametallic complexes

[M8(C4O7)4(H2O)12]?24H2O (M = Zn, Co, Fe or Mg), formed during reactions of the

metal(II) acetates with dihydroxyfumaric acid in aqueous solution.81 The cubane-

type core of the complexes comprise four M(II) ions and four m3-alkoxo centres from

separate [C4O7]42 anions, additionally each carboxy group of the tetraanion binds to

each one of the three metal ions that are bridged by the alkoxo centre. Small-angle

X-ray scattering analysis of poly(carbon suboxide), (C3O2)n confirms that in solution

the structure is poly(a-pyronic), the value of n (#40) suggests a one-dimensional

bandlike structure.82 The [5,6]-open isomer of C60O dimerises readily to give a C2

symmetric adduct C120O2, in which the cages are linked by two single bonds between

the sp3 hybridised carbons adjacent to the oxygen atoms.83 The absorption spectrum

of C120O2 in toluene is red-shifted relative to C120, while photodissociation of the

dimer occurs under comparatively mild conditions.

Two tetraorganoammonium superoxide salts, [NMe3Ph][O2] and [NBu4][O2] are

available from ion-exchange reactions in liquid ammonia.84 The [NMe3Ph]+ salt

contains an almost completely unperturbed superoxide anion as judged by d(O–O)

[1.332(2) A], since weakly bonding interactions in the solid state are absent, whereas

in the [NBu4]+ salt hydrogen-bonded ammonia solvate molecules draw electron

density from the anion shortening d(O–O) to 1.312(2) A. New non-photolytic routes

to dihydrogen trioxide (H2O3) have been developed by passage of an O3–O2 stream

through 96% aqueous hydrogen peroxide and by ozonolysis of a resin-supported

diphenylhydrazine, in each case at 278 uC;85 characterisation was by 1H NMR,



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dH 13.6 at 260 uC. An ab initio analysis of the hypothetical anion [O4]22, which

is isoelectronic with [ClO3]2 and [SO3]22, suggests that the gas-phase molecule

[FLi3][O4] is metastable and may ultimately be accessible.86 The reaction of CF3?

with CO/O2 gives the peroxide CF3OC(O)OOC(O)OCF3, via an intermediate

trioxide CF3OC(O)OOOC(O)OCF3, a process studied by FTIR spectroscopy using

isotopically labelled reagents.87 The same group also explored bis(fluoroformyl)-

trioxide, FC(O)OOOC(O)F.88

The binding of dioxygen to metal complexes has received extensive attention, in

the interests of brevity a limited number of examples are cited. Theoretical

calculations suggest that the preparation and study by matrix isolation spectroscopy

of [F2Al(m-g2:g2-O2)AlF2] should be possible.89 A monomeric nickel–dioxygen

adduct [NiIIL(O2)] was prepared from [NiIL(CO)] and dioxygen [L = phenyltris{(1-

adamantylthio)methyl}borate] at 270 uC.90 EXAFS and EPR spectroscopies and

DFT calculations reveal a highly covalent nickel(II)–superoxo structure with side-on

bonding. [CoIII(tmen)2(O2)][ClO4], generated by reacting cobalt(II) salts with

hydrogen peroxide in the presence of tmen, is a rare example of a crystallographically

characterised g2-peroxo complex whose co-ligands have saturated backbones.91

Stable for prolonged periods as a solid and in aqueous solution, protonation

with perchloric acid generates cis-[Co(tmen)2(OH2)2]3+. The diplatinaborane

[(PMe2Ph)4Pt2B10H10] reversibly binds atmospheric dioxygen at the metal centres

to give the fluxional adduct [(PMe2Ph)4Pt2(g2-O2)B10H10] which was characterised

crystallographically.92 The reactivity and structural spectroscopic features of

copper–dixoygen complexes, with an emphasis on models of biological systems,

have been reviewed.93,94

Oxo clusters are as structurally diverse as those of the heavier chalcogens. 17O

NMR studies of peroxotungstates over the pH range 0.5–9.0 show that the main

cluster generated from the oxidation of tungsten powder with 30% aqueous hydrogen

peroxide is the symmetrical anion [W6O13(OH)2(OH2)2(O2)5]22.95 The reaction of

[MoO4]22 with periodic acid gives [(IMo7O26)2]62, a cluster described by the authors

as a missing link between molecular and solid oxides, which was isolated as the

[NBu4]+ salt.96 The oxygen, water and hydroxyl environments of the monoproto-

nated hexaniobate Na7[HNb6O19]?15H2O were probed by 1H and 17O MAS NMR,

which demonstrate that the proton is situated on the bridging oxygen of the cluster,

while solution 17O NMR gives an insight into the oxygen positional exchange

processes occurring.97 Triple-cubane clusters [{Ru(g6-arene)}4Mo4O16] were pre-

pared by treatment of the molybdates Na2[MoO4]?2H2O and [NBu4]2[Mo2O7] with

[Ru(g6-arene)Cl(m-Cl)]2 in aqueous or organic solvents.98 The p-cymene derivative

underwent partial isomerisation to the more thermodynamically stable ‘‘windmill’’

form under forcing conditions. Treatment of platinum(II) nitrate with concentrated

sulfuric acid at 350 uC gives a cluster anion [Pt12O8(SO4)12]42, constructed by the

binding of six [Pt2]6+ ions by oxide and sulfate groups.99 An oxysulfide–oxysulfate

dioxygen storage mechanism was found in the sulfur redox cycle between La2O2SO4

(S6+) and La2O2S (S22) phases.100 The dioxygen storage capacity (2 mol O2 mol21) is

eight times greater than for CeO2–ZrO2, and is unusual in the utilisation of sulfur as

the redox centre instead of a metal ion.

Two structurally different hexameric stannoxanes are accessible by treatment ofnBu2Sn(O) or nBuSn(O)OH with 3,5-diisopropylsalicylic acid.101 The dibutyl

compound reacts to give a complex which has a very rare cyclic hexameric structure

with an Sn6O18 macrocycle and a tbp arrangement at the metal centres, whereas the



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product from the stannoic acid precursor possesses the more commonly observed

drum-like motif with hexacoordinate Sn(IV). The phosphinidene oxide ligand

(supermes)PLO is P-monodentate in [MoCp{g1-P(O)(supermes)}(CO)2]2, upon

treatment with electrophiles (MeI, allyl bromide) alkylation at the phosphorus

centre gives complexes with an Mo–O–P ring.102 Neutral and zwitterionic

titanium and hafnium alkyl complexes with the boroxide ligand [Mes2BO]2, which

is formally analogous to an alkoxide, have been identified as potential ethylene

polymerisation catalysts.103

Ligand/reagent abbreviations used in this chapter

Ad 1-adamantyl

Bpq 59,5--bis(2,6-diisopropylphenyl)-2,6,200,600-tetraisopropyl-m-

quinquephenyl-20-yl

Ditp 2,20-diisopropyl-m-terphenyl-29-yl

dpph Ph2P(CH2)6PPh2

dpppe Ph2P(CH2)5PPh2

Mes 2,4,6-Me3C6H2

Supermes 2,4,6-tBu3C6H2

Tbt 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl

References

1 M. C. Aragoni, M. Arca, F. Demartin, F. A. Devillanova, A. Garau, P. Grimaldi, F. Isaia,F. Lelj, V. Lippolis and G. Verani, Eur. J. Inorg. Chem., 2004, 2363.

2 M. C. Aragoni, M. Arca, M. B. Carrea, F. Demartin, F. A. Devillanova, A. Garau,F. Isaia, V. Lippolis and G. Verani, Eur. J. Inorg. Chem., 2004, 4660.

3 F. Bigoli, M. C. Cabras, P. Deplano, M. L. Mercuri, L. Marchio, A. Serpe and E. F. Trogu,Eur. J. Inorg. Chem., 2004, 960.

4 M. C. Aragoni, M. Arca, F. Demartin, F. A. Devillanova, F. Lelj, F. Isaia, V. Lippolis,A. Mancini, L. Pala and G. Verani, Eur. J. Inorg. Chem., 2004, 3099.

5 W. Nakanishi, S. Hayashi, S. Yamaguchi and K. Tamao, Chem. Commun., 2004, 140.6 G. N. Ledesma, E. S. Lang, E. M. Vazquez-Lopez and U. Abram, Inorg. Chem. Commun.,

2004, 7, 478.7 L. Lee, D. J. Crouch, S. P. Wright, R. Berridge, P. J. Skabara, N. Bricklebank, S. J. Coles,

M. E. Light and M. B. Hursthouse, CrystEngComm., 2004, 6, 612.8 S. Kumar, K. Kandasamy, H. B. Singh and R. J. Butcher, New J. Chem., 2004, 28, 640.9 M. Iwaoka, H. Kornatsu, T. Katsuda and S. Tomoda, J. Am. Chem. Soc., 2004, 126, 5309.

10 S. Kumar, K. Kandasamy, H. B. Singh, G. Wolmershauser and R. J. Butcher, Organo-metallics, 2004, 23, 4199.

11 H. Poleschner and K. Seppelt, Chem. Eur. J., 2004, 10, 6565.12 T. M. Klapotke, B. Krumm and K. Polborn, J. Am. Chem. Soc., 2004, 126, 710.13 T. M. Klapotke, B. Krumm, J. C. Galvez-Ruiz, H. Noth and I. Schwab, Eur. J. Inorg.

Chem., 2004, 4764.14 T. M. Klapotke, B. Krumm, K. Polborn and I. Schwab, J. Am. Chem. Soc., 2004, 126,

14166.15 J. Passmore and C. Knapp, Angew. Chem., Int. Ed., 2004, 43, 4834.16 T. M. Klapotke, B. Krumm and P. Mayer, Z. Naturforsch., Teil B, 2004, 59, 547.17 H. Fleischer, S. Glang, D. Schollmeyer, N. W. Mitzel and M. Buhl, Dalton Trans., 2004,

3765.18 J. Meija and J. A. Caruso, Inorg. Chem., 2004, 43, 7486.19 V. Munchow and R. Steudel, Eur. J. Inorg. Chem., 2004, 718.20 I. P. Gray, A. M. Z. Slawin and J. D. Woollins, New J. Chem., 2004, 28, 1383.21 J. Nakayama, S. Aoki, J. Takayama, A. Sakamoto, Y. Sugihara and A. Ishii, J. Am. Chem.

Soc., 2004, 126, 9085.22 R. Steudel and Y. Steudel, Eur. J. Inorg. Chem., 2004, 3513.



Publ

ishe

d on

14

Mar

ch 2

005.

Dow

nloa

ded

by T

empl

e U

nive

rsity

on

29/1

0/20

14 1

5:10

:54.

View Article Online


23 M. C. McCarthy, S. Thorwirth, C. A. Gottlieb and P. Thaddeus, J. Am. Chem. Soc., 2004,126, 4096.

24 K. Okuma, T. Shigetani, Y. Nibu, K. Shioji, M. Yoshida and Y. Yokomori, J. Am. Chem.Soc., 2004, 126, 9508.

25 M. L. Golden, J. C. Yarbrough, J. H. Riebenspies and M. Y. Darensbourg, Inorg. Chem.,2004, 43, 4702.

26 S. M. Nahri, R. Oilunkaniemi, R. S. Laitinen and M. Ahlgren, Inorg. Chem., 2004, 43,3742.

27 M. Majasato, T. Sagami, M. Minoura, Y. Yamamoto and K. Akiba, Chem. Eur. J., 2004,10, 2590.

28 F. DeProft, P. W. Fowler, R. W. A. Havenith, P. von Rague-Schleyer, G. VanLier andP. Geerlings, Chem. Eur. J., 2004, 10, 940.

29 H. M. Tuonenen, R. Suontamo, J. Valkonen and R. S. Laitinen, J. Phys. Chem. A, 2004,108, 5670.

30 D. Leusser, J. Henn, N. Kocher, B. Engels and D. Stalke, J. Am. Chem. Soc., 2004, 126,1781.

31 T. Borrmann, E. Lork, R. Mews, M. M. Shakirov and A. B. Zibarev, Eur. J. Inorg. Chem.,2004, 2452.

32 T. Maaninen, H. M. Tuononen, G. Schatte, R. Suontamo, J. Valkonen, R. Laitinen andT. Chivers, Inorg. Chem., 2004, 43, 2097.

33 M. J. Crawford, T. M. Klapotke, P. Mayer and M. Vogt, Inorg. Chem., 2004, 43, 1370.34 J. L. Brusso, O. P. Clements, R. C. Haddon, M. E. Itkis, A. A. Leitch, R. T. Oakley,

R. W. Reed and J. F. Richardson, J. Am. Chem. Soc., 2004, 126, 8256.35 J. L. Brusso, O. P. Clements, R. C. Haddon, M. E. Itkis, A. A. Leitch, R. T. Oakley,

R. W. Reed and J. F. Richardson, J. Am. Chem. Soc., 2004, 126, 14692.36 L. Beer, J. F. Britten, O. P. Clements, R. C. Haddon, M. E. Itkis, K. M. Matkovich,

R. T. Oakley, R. W. Reed and J. F. Richardson, Chem. Mater., 2004, 16, 1564.37 H. J. Dieseroth, M. Wagener and E. Neumann, Eur. J. Inorg. Chem., 2004, 4755.38 F. Wendland, C. Nather and W. Bensch, Z. Naturforsch., Teil B, 2004, 59, 629.39 P. Sekar and J. A. Ibers, Inorg. Chem., 2004, 43, 5436.40 A. Baumann and J. Beck, Z. Anorg. Allg. Chem., 2004, 630, 2078.41 I. Krossing and J. Passmore, Inorg. Chem., 2004, 43, 1000.42 E. Alessio, Chem. Rev., 2004, 104, 4205.43 M. Calligaris, Coord. Chem. Rev., 2004, 248, 351.44 K. E. Holmes, P. F. Kelly and M. R. J. Elsegood, Dalton Trans., 2004, 3488.45 K. E. Holmes, P. F. Kelly and M. R. J. Elsegood, CrystEngComm., 2004, 6, 56.46 I. P. Gray, A. M. Z. Slawin and J. D. Woollins, Z. Anorg. Allg. Chem., 2004, 630, 1851.47 C. S. Lai and E. R. T. Tiekink, CrystEngComm., 2004, 6, 593.48 C. S. Lai, S. Liu and E. R. T. Tiekink, CrystEngComm., 2004, 6, 221.49 J. K. Bjernemose, R. P. Davies, A. P. S. Jurd, M. G. Martinelli, P. R. Raithby and

A. J. P. White, Dalton Trans., 2004, 3169.50 X. Ribas, J. C. Dias, J. Morgado, K. Wurst, M. Almeida, T. Parella, J. Veciana and

C. Rovira, Angew. Chem., Int. Ed., 2004, 43, 4049.51 X. Ribas, D. Maspoch, J. Dias, J. Morgado, M. Almeida, K. Wurst, G. Vaughan,

J. Veciana and C. Rovira, CrystEngComm., 2004, 6, 589.52 S. M. Aucott, H. L. Milton, S. D. Robertson, A. M. Z. Slawin and J. D. Woollins, Dalton

Trans., 2004, 3347.53 S. M. Aucott, H. L. Milton, S. D. Robertson, A. M. Z. Slawin, G. D. Walker and

J. D. Woollins, Chem. Eur. J., 2004, 10, 1666.54 C. M. Standfest-Hauser, K. Mereiter, R. Schmid and K. Kirchner, Organometallics, 2004,

23, 2194.55 N. J. Hill, W. Levason, R. Patel, G. Reid and M. Webster, Dalton Trans., 2004, 980.56 C. J. Burchell, S. M. Aucott, H. L. Milton, A. M. Z. Slawin and J. D. Woollins, Dalton

Trans., 2004, 369.57 K. A. Rufanov, B. Ziemer and M. Meisel, Dalton Trans., 2004, 3808.58 D. Wechsler, R. McDonald, M. J. Ferguson and M. Stradiotto, Chem. Commun., 2004,

2446.59 C. W. Liu, C. M. Hung, B. K. Santra, Y. H. Chu, J. C. Wang and Z. Lin, Inorg. Chem.,

2004, 43, 4306.60 B. K. Santra, C. M. Hung, B. J. Liaw, J. C. Wang and C. W. Liu, Inorg. Chem., 2004, 43,

7570.61 B. K. Santra, B. J. Liaw, C. M. Hung, C. W. Liu and J. C. Wang, Inorg. Chem., 2004, 43,

8866.



Publ

ishe

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14

Mar

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Dow

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nive

rsity

on

29/1

0/20

14 1

5:10

:54.

View Article Online


62 M. K. Brandmeyer, R. Clerac, F. Wiegend and S. Dehnen, Chem. Eur. J., 2004, 10, 5147.63 J. Olkowska-Oetzel, P. Sevillano, A. Eichhofer and D. Fenske, Eur. J. Inorg. Chem., 2004,

1080.64 V. Jancik, M. N. M. Cabrera, H. W. Roesky, R. Herbst-Irmer, D. Neculai, A. M. Neculai,

M. Noltemeyer and H. G. Schmidt, Eur. J. Inorg. Chem., 2004, 3508.65 Y. Peng, H. Fan, V. Jancik, H. W. Roesky and R. Herbst-Irmer, Angew. Chem., Int. Ed.,

2004, 43, 6190.66 A. J. Hulkes, A. F. Hill, B. A. Nasir, A. J. P. White and D. J. Williams, Organometallics,

2004, 23, 679.67 M. N. Sokolov, A. L. Gushchin, A. V. Virovets, E. V. Peresypkina, S. G. Kozlova and

V. P. Fedin, Inorg. Chem., 2004, 43, 7966.68 C. Magliocchi, X. Xie and T. Hughbanks, Inorg. Chem., 2004, 43, 1902.69 R. Hernandez-Molina, M. Sokolov, P. Esparza, C. Vicent and R. Llusar, Dalton Trans.,

2004, 847.70 M. L. Kuhlman and T. B. Rauchfuss, Organometallics, 2004, 23, 5085.71 T. Chivers and D. J. Eisler, Angew. Chem., Int. Ed., 2004, 43, 6686.72 M. Saito, N. Tokitoh and R. Okazaki, J. Am. Chem. Soc., 2004, 126, 15572.73 Y. Kim and S. W. Martin, Inorg. Chem., 2004, 43, 2773.74 I. Chung, J. Do, C. G. Canlas, D. P. Weliky and M. G. Kanatzidis, Inorg. Chem., 2004, 43,

2762.75 L. M. Wu and D. K. Seo, J. Am. Chem. Soc., 2004, 126, 4676.76 P. Vaqueiro, A. M. Chippindale and A. V. Powell, Inorg. Chem., 2004, 43, 7963.77 G. Lente and I. Fabian, Inorg. Chem., 2004, 43, 4019.78 J. J. Barnett, M. L. McKee and D. M. Stanbury, Inorg. Chem., 2004, 43, 5021.79 K. Shimada, K. Goto, T. Kawashima, N. Takagi, Y. K. Choe and S. Nagase, J. Am.

Chem. Soc., 2004, 126, 13238.80 M. Gonsior and I. Krossing, Chem. Eur. J., 2004, 10, 5730.81 B. F. Abrahams, T. A. Hudson and R. Robson, J. Am. Chem. Soc., 2004, 126, 8624.82 M. Ballauff, S. Rosenfeldt, N. Dingenouts, J. Beck and P. Krieger-Beck, Angew. Chem.,

Int. Ed., 2004, 43, 5843.83 D. Tsyboulski, D. Heymann, S. M. Bachilo, L. B. Alemany and R. B. Weisman, J. Am.

Chem. Soc., 2004, 126, 7350.84 P. D. C. Dietzel, R. K. Kremer and M. Jansen, J. Am. Chem. Soc., 2004, 126, 4689.85 P. T. Nyfeller, N. A. Boyle, L. Eltepu, C. H. Wong, A. Eschenmoser, R. A. Lerner and

P. Wentworth, Angew. Chem., Int. Ed., 2004, 43, 4656.86 B. M. Elliott and A. I. Boldyrev, Inorg. Chem., 2004, 43, 4109.87 M. A. B. Paci and G. A. Arguello, Chem. Eur. J., 2004, 10, 1838.88 H. Pernice, M. Berkei, G. Henkel, H. Willner, G. A. Arguello, M. L. McKee and

T. R. Webb, Angew. Chem., Int. Ed., 2004, 43, 2843.89 A. Hammerl, B. J. Welch and P. Schwerdtfeger, Inorg. Chem., 2004, 43, 1436.90 K. Fujita, R. Schenker, W. Gu, T. C. Brunold, S. P. Cramer and C. G. Riordan, Inorg.

Chem., 2004, 43, 3324.91 A. F. M. M. Rahman, W. G. Jackson and A. C. Willis, Inorg. Chem., 2004, 43, 7558.92 J. Bould, Y. M. McInnes, M. J. Carr and J. D. Kennedy, Chem. Commun., 2004, 2380.93 E. A. Lewis and W. B. Tolman, Chem. Rev., 2004, 104, 1047.94 L. M. Mirica, X. Ottenwaelder and T. D. P. Stack, Chem. Rev., 2004, 104, 1013.95 O. W. Howarth, Dalton Trans., 2004, 476.96 D. Honda, T. Ozeki and A. Yagasaki, Inorg. Chem., 2004, 43, 6893.97 T. M. Alam, M. Nyman, B. R. Cherry, J. M. Segall and L. E. Lybarger, J. Am. Chem. Soc.,

2004, 126, 5610.98 D. Laurencin, E. G. Fidalgo, R. Villanneau, F. Villain, P. Herson, J. Pacifico, H. Stoeckli-

Evans, M. Benard, M. M. Rohmer, G. Suss-Fink and A. Proust, Chem. Eur. J., 2004, 10,208.

99 M. Pley and M. S. Wickleder, Angew. Chem., Int. Ed., 2004, 43, 4168.100 M. Machida, K. Kawamura and K. Ito, Chem. Commun., 2004, 662.101 G. Prabusankar and R. Murugavel, Organometallics, 2004, 23, 5644.102 M. Alonso, M. E. Garcia, M. A. Ruiz, H. Hamidor and J. C. Jeffery, J. Am. Chem. Soc.,

2004, 126, 13610.103 S. C. Cole, M. P. Coles and P. B. Hitchcock, Dalton Trans., 2004, 3428.



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7 oxygen, sulfur, selenium and tellurium

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