7 Oxygen, Sulfur, Selenium, and Tellurium

J. DEREK WOOLLINS

Leicestershire, L E 1 7 3TU, UK Department of Chemistry, Loughborough University of Technology, Loughborough,

A number of significant reviews were published in 1994. A very good account of the properties and uses of Group 13 oxides and hydroxides' will be of wide interest. The importance of oxides in materials was highlighted. Thus, there were reviews on the characterization of hybrid siloxane-oxide materials obtained from sol-gel processing,2 an account of volatile metallo-organic precursors for the deposition of inorganic electronic material^,^ as well as a discussion of heterometallic alkoxides and oxoalkoxides used in chemical routes (e.y. hydrolysis) to metal oxide^.^

Heavier Group 16 elements are also relevant in materials science and there were useful reviews on a number of topics. Several reactions have been described which illustrate how molecular reagents (e.g. M(ER), M = Zn, Cd, Hg: E = S, Se, Te; R = alkyl, aryl) can be transformed into extended inorganic solids.' An interesting paper on a related topic was presented at the American Chemical Society meeting.6 The growing interest in S-N-P polymers was well illustrated in an excellent review by manner^.^ Supposedly 'simple' systems also continue to be studied. Thus homo- and hetero-atomic Group 16 rings were reviewed.' There were also reviews on the coordination chemistry of PNS and PNSe rings/cages which demonstrate mono-, di-, tri-, and tetra-dentate b ~ n d i n g . ~ The innovative recent work in Se-N and Te-N chemistry has also been summarized."

There continues to be very substantial interest in the biological aspects of sulfur and selenium chemistry which largely falls outside the remit of this report. Typical examples include' ' the study of the degradation of thiosulfate and tetrathionate by Thiobacillus- intermedius. A NMR study of the interaction of platinum salts with tetrapeptide- containing cysteinyl residues' showed cis-Pt(NH,),Cl, to coordinate (with displace-

' K. A. Evans, 'Chem. Alum., Gallium, Indium, Thallium', 1993,248, ed. A. J. Downs, Blackie, Glasgow, 1994. F. Babonneau, Polyhedron, 1994, 13, 1123. D. C. Bradley, Polyhedron, 1994, 13, 11 11. L. G. Hubert-Pfalzgraf, Polyhedron, 1994, 13, 1181.

H.W. Roesky, Abs. Am. Chem. Soc., 1994, 208, 174-INOR.

R. S. Laitinen, P. Pekonen, and R. J . Suontamo, Coord. Chem. Rev., 1994, 130, 1. T. Chivers and R.W. Hilts, Coord. Chem. Rev., 1994, 137, 201.

S. Wentzien, W. Sand, A. Albertsen, and R. Steudel, Arch. Microhiol., 1994 161, 116.

' M. L. Steigerwald, Polyhedron, 1994, 13, 1245.

' I. Manners, Coord. Chem. Rev., 1994, 137, 109.

lo A. Haas, J. Kasprowski, and M. Pryka, Coord. Chem. Rev., 1994, 130, 301.

'' N. Hadjiliadis, N. Ferderigos, J. L. Butour, H. Marzarguil, G. Gasmi, and J. P. Laussac, Inorg. Chem., 1994, 33, 5057.

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94 J . Derek Woollins

ment of the chloride) with the -S-CH, groups of the tetrapeptide; upon coordination there is NH, liberation as a consequence of the strong trans effect of the S-donor ligands.

Studies on bioinorganic enzymes continue in many areas. For example, a new analysis of the EPR and Mossbauer data in nitrogenase P-clusters suggested that each half of the cluster contains a 'classical' [Fe,S,] + unit with one Fe"' and three Fe" sites but that as a consequence of an additional serine ligand at one site the spin properties of the two halves are different.I3

The Ni" dinuclear site of urease (jack bean) has been studied by EXAFS with and without 2-mercaptoethanol. The 2-mercaptoethanol-containing dinuclear site is proposed to contain two Ni" ions bridged by the thiolate sulfur atoms of the thiols. l4 There was an interesting review on the role of selenium in micro- organism^,'^ furthermore there have been numerous reports on selenium in biological and/or environmental systems. For example, supplementation of a normal diet with additional selenium was shown16 to modulate T-lymphocyte mediated immune responses in humans where the responses depend on signals generated by the interaction of interleukin 2. The use of two selenium-containing fertilizers has been evaluated,17 surprisingly the authors suggest that BaSeO, provides an effective alternative to current strategies for supplying selenium to grazing animals. A study of contaminants in eggs in California showed that although selenium levels were supposedly high enough to cause reproductive problems no impairment was observed in these cases.I8 Studies on metallathionen levels in rats fed or injected with selenite showed that feeding the animals 5-9pg/g of Se as selenite had no impact whereas injections of 1.5 mg/g Se as selenite did increase metallathionen levels in the liver and kidney, although not as markedly as when zinc is used." One can only hope that studies of this type provide some genuinely useful insights.

Singlet oxygen chemistry continues to be of great interest both from fundamental and applied perspectives. Thus, the singlet oxygen quantum yields from the triplet excited states of D N A and related molecules have been studied; interestingly for guanine-containing moieties, no singlet oxygen was detected; some possible implica- tions relating to D N A photodamage were discussed.20

Ozonolysis of c60 generates a mixture of oxidized products with ketone, ester, and epoxide functionalities;2 one imagines that c60 would also react successfully with s g

to give equally interesting products. The report of non-reactivity of C,, with chemically generated singlet oxygen22 further serves to illustrate the chemical community's remarkable interest in C,, chemistry; although no reactions with graphite were reported.

Many other ozonolysis reactions have also been reported, for example reactions with

l 3 J. M. Mouesca, L. Noodleman, and D. A. Case, Inorg. Chem., 1994,33, 4819. l4 S. Wang, M. H. Lee, R . P. Hausinger, P. A. Clark, D. E. Wilcox, and R. A. Scott, Inorg. Chem., 1994, 33,

1589. J . Heider and A. Boeck, Ado. Microh. Physiol., 1993, 35, 71.

1994, 41, 103. l 6 M. Roy, L. Kiremidjian-Schumacher, H. L. Wishe, M. W. Cohen, and G. Stotzky, Biol. Truce Elem. Res.,

l 7 B. R. Whelan, D. W. Peter, and N . J . Barrow, Aust. J. Agric. Res., 1994, 45, 863. '' R. L. Hotherm and D. Welsh, Arch. Enuiron. Contam. Toxicol., 1994, 27, 180. l 9 C. L. Chen and P. D. Whanger, J. Inorg. Biochem., 1994,54, 267. 2 o S. M. Bishop, M. Malone, D. Phillips, A. W. Parker, and M. C. R . Symons, J . Chem. Soc., Chem. Commun.,

2 1 M. Ripudaman, S. Kumar, and A. Satyam, J. Chem. SOC., Chem. Commun., 1994, 1339. 2 2 L. Juha, V. Hamplova, J. Kodymova, and 0. Spalek, J . Chem. SOC., Chem. Commun., 1994, 2437.

1994, 871.

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Oxygen, Sulfur, Selenium, and Tellurium 95

ferro- and ferri-cyanides in the solid state have been discussed.23 Simple binary compounds continue to be worthy of study. Density function

calculations on S,O, indicate that there are numerous 'stable' cyclic structures although it is clear that S=O is preferable to S-0-S and that an S, chair conformation is better than a boat c~nformation. '~ The structures of [HS,O,] - and [ClSO,] - have been calculated. SO, and HS- should form a chain-like [HSSO,] - (exothermic by ca. 108 kJmol-') whilst SO, + C1- --+ [ClSO,]- is also exothermic (79 kJmol-').25

A number of interesting metal oxygen systems have been reported. Cyclic metallasilozanes based on, for example, (Bu\)Si(OH), are readily prepared26 and a number of examples were characterized crystallographically. In related work the acyclic phosphazene ligand HN(P(NMe,),NSiMe,}, was reacted with [NH,]VO, to give the [VO,(SiMe,),]- anion in quantitative yield.27 The SiMe, groups migrate from N to 0 centres in this reaction.

Reaction of MoCI,(PMe,), with neutral sulfur donor ligands (e.g. SPPh,) gives Mo,(p-S)(p-Cl)(PMe,),, formed via Mo(S)Cl,(PMe,),, which undergoes a con- proportionation reaction with the starting material.28 The Mo-S distance in the Mo"'-Mo"' bi-octahedral product is 2.276( 1) A. The synthesis of terminal vanadium imido, 0x0, sulfido, selenido, and tellurido complexes has been reported.29

Oxidation reactions, both stoichiometric and catalytic, have continued to excite interest. Thus, CoCl,/acetonitrile was shown to be a good mimic for B12 for the conversion of sulfides into di~ulfides.~' New porphyrins containing electron-with- drawing p-substituents have been prepared, the Fe"' complex was shown to be an excellent catalyst for the epoxidation of cycl~octene.~ Regioselective hydroxylation of phenols has been reported using a ~erium'~-calix(8)arene.~~ The use of palladium catalysts for the oxidation of allylic amines with molecular oxygen appears to be solvent dependent with Me,SO being especially useful.,,

Rh salts have proved34 to be valuable for the selective transformation of saturated hydrocarbons into alkyl trifluoroacetates by treatment with H,O, and CF,CO,H. A new ruthenium complex35 [R~O,(bipy)(I0,)(0H)~]l .5H20 has been characterized by X-ray crystallography (Figure 1) and shown to be an efficient catalyst for alkene epoxidation and the oxidation of primary and secondary alcohols to aldehydes and ketones respectively. Ruthenium was also used to catalyse the oxidation of chlorinated olefins by mon~per su l f a t e~~ at room temperature and for the aerobic oxidation of alcohols.37

2 3 E. Reguera, J. Fernandez-Bertran, and J. Duque, Polyhedron, 1994, 13, 479. 24 R.O. Jones, Inorg. Chem., 1994,33, 1340. 2 5 K. Miaskiewicz and R. Steudel, J. Chem. Soc., Dalton Trans., 1994, 2919. 26 H. J. Gosink, H. W. Roesky, H. G. Schmidt, M. Noltemeyer, E. Irmer, and R. Herbstirmer, Organometallics,

27 S. K . Pandey, H. W. Roesky, D. Stalke, A. Steiner, H. G. Schmidt, and M. Noltemeyer, Phosphorus Sulfur 1994,13, 3420.

Silicon Relat. Elem., 1993, 84, 231. K . A . Hall and R. J. M. Maye, Inorg. Chem., 1994, 33, 3289.

29 C.C. Cummins, R. R. Schrock, and W. M. Davis, Inorg. Chem., 1994, 33, 1448. 30 S. Chowdhury, P.M. Samuel, I. Das, and S. Roy, J. Chem. Soc., Chem. Commun., 1994, 1993. 3 1 J. F. Bartoli, P . Battioni, W.R. De Foor, and D. Mansuy, J. Chem. SOC., Chem. Commun., 1994, 23. 32 H. M. Chawla, U. Hooda, and V. Singh, J . Chem. SOC., Chem. Commun., 1994, 617. 3 3 R. A. T. M. van Benthem, H. Hiemstra, J. J. Michells, and W. N. Speckamp, J. Chem. Soc., Chem. Commun.,

34 K. Nomura and S. Uemura, J . Chem. SOC., Chem. Commun., 1994, 129. 35 A. J. Bailey, W. P. Griffiths, A. J. P. White, and D. J. Williams, J. Chem. Soc., Chem. Commun., 1994, 1833. 36 M. Bressan, L. Forti, and A. Morvillo, J. Chem. SOC. , Chem. Commun., 1994, 253. 37 S.Y. S. Cheng, N. Rajapakse, S. J. Rettig, and B. R. James, J. Chem. SOC., Chem. Commun., 1994, 2669.

1994, 357.

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96 J . Derek Woollins

Figure 1 The X-ray structure of [RuO,(bipy){IO,(OH),~]~l SH,O

Polytungstates were shown to be useful for the aerobic oxidation of H,S to Na[P,W,,O, appears to give higher purity S, than the iron complexes which are currently used commercially. The influence of S-N-0 species on the redox behaviour of Mn"'"' species has also been studied.39

Solid state catalysts have also been studied. Thus, zeolites were used4' for the catalytic oxidation of arylamines to azoxybenzenes with H,O,. Direct hydrothermal synthesis was used to furnish a new large pore titanium silicate which is a useful catalyst for the selective oxidation of hydrocarbon^.^^

New 0x0 and dioxygen complexes have been reported. Thus the reaction of FeCl,/RNH/CO, yields N-dialkylcarbamato complexes of Fe" such as { [Fe(O,(CNEt,),},]. Controlled hydrolysis of these compounds gave, for example, [{Fe(p,-O)(O,CNPr\),], which exists with two Fe, tetrahedra, face to face and an unusual ( p 4 0 ) bridge4, (Figure 2). Photolysis of [((Fe(edta)} ,014- gives oxygen and [Fe"(edta)12 - ; this was rationalized by proposing a Fe"=O Intermediate.43

Stable peroxo complexes of osmium (Equation 1) were obtained by addition of 0, to [OsX(dcpe),]+ (X = C1 or H, dcpe = 1,2-bis(dicy~lohexylphosphine)ethane).~~

[OsX(dcpe),] + + 0, -+ truns-[OsX(O,)(d~pe)~] + (1 1 Novel 0x0-persulfido tungstate complexes were reported from the reaction of WSi-

with P2S,H,NNH,-2HC1 in CH,CN; WO(S,),{CH,C(=NH)NHNH} contains a terminal W=O, two S i - ligands, and a bidentate amidrazone ligand.45 Mono- oxomolybdenumIv dithiolato complexes have been prepared and studied as models for ox idoredu~tases .~~ Larger ring and cluster 0x0 complexes were also studied. Thus, a

3 8 M.K. Harrup and C.L. Hill, Inorg. Chem., 1994, 33, 5448. 3 9 F.F. Prinsloo, J. J. Pienaar, R. Vaneldik, and H. Gutberlet, J . Chem. Soc., Dalton Trans., 1994, 2373. 40 H. R. Sonawane, A. V. Pol. P. P. Moghe, S. S. Biswas, and A. Suydalai, J . Chem. SOC. , Chem. Commun., 1994,

" A. Corma, M.T. Navarro, and J. P. Pariente, J . Chem. Sor., Chem. Commun., 1994, 147. '* D. B. Dell'Amico, F. Calderazzo, L. Labella, C. Maichel-Mossmer, and J. Strahle, J . Chem. Soc., Chem.

4 3 H. Kunkely and A. Vogler, J . Chem. Soc., Chem. Commun., 1994, 2671. '4 A. Mezzetti, E. Zangrando, A. Del Sotto, and P. Rigo, J . Chem. SOC. , Chem. Commun., 1994, 1597. 4 5 S. Du, N. Zhu, and X. Wu, Polyhedron, 1994, 13, 301. 46 K. Yamanari, M. Mori, S. Dogi, and A. Fuyuhiro, Inorg. Chem., 1994, 33, 4807. 47 H. Oku, N. Ueyama, M. Kondo, and A. Nakamura, Inorg. Chem., 1994, 33, 209.

1215.

Commun., 1994, 1555.

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Oxygen, Sulfur, Selenium, and Tellurium 97

Figure 2 The X-ray structure4' of [{ Fe4(p,-O)(0,CNPr!J,),1

systematic study upon M,[TeMo60,,].nH,0 [M = di- and tri-valent metals] has been reported.48 A range of doubly bridged dinuclear Co"' peroxo complexes were de~cribed.,~ A novel Mo,O,Cl,(~,-O),(~,-Eto)6(~2-cl)~ metallacycle exhibits49 a unique chair arrangement of the metal atoms with three Mo-Mo single bonds and two Mo,(p3-O) bridges. The reaction of ammonium vanadate with sodium molybdate in acidic aqueous solution followed by addition of morphine gives5' [Hmorph][Mo,V,- O,,]Cl, which is built up of nine edge-sharing Mo, octahedra with a random distribution of Mo and V atoms in the two 'capping' sites.

The solid state reaction of [NH,],Mo7O2,.4H,O with [Bu,N]Br and NH,OH.HCl at 90°C gives [BU~N], [H,O]~[MO, ,O~~]~ which contains two [MO,,O,,]~- anions with Keggin-type structures although the anions have different ~ymmetry.~' Other reports in this area include work on undecatungst~arsenates,~~

The crystal structure of trans-VOCl,(H,O), hydrogen bonded adducts with two crown ethers have been compared,,, the 0-V-0 angles were ca. 153". Solid phase

[Cp*TiMo,O 8 ] - ,53 [M08026]4- ,54 and [NaMO,O,,] - ."

A. Saito, Inory. Chim. Acta, 1994, 217, 93.

B. Kamenar, M . Cindric, and N. Strukan, Polyhedron, 1994, 13, 2271. 49 C. Limberg, S. Parsons, and A. J. Downs, J . Chem. SOC., Chem. Commun., 1994, 497.

s 1 X. Jin, K. Tang, H. Ni, and Y. Tang, Polyhedron, 1994, 13, 2439. 5 2 J. Liu, W. Wang, G. Wang, B. Zhao, and S . Sun, Polyhedron, 1994, 13, 1057. 53 H. Akashi, J. Chen, T. Sakuraba, and A. Yagasaki, Polyhedron, 1994, 13, 1091. " M. McCann and K. Maddock, Polyhedron, 1994, 13, 835. s 5 A.N. Startsev, O.V. Klimov, S.A. Shkuropat, M.A. Fedotov, S .P . Degtyarev, and D.I. Kochubey,

5 6 N. Azuma and T. Ozawa, Polyhedron, 1994, 13, 1715. Polyhedron, 1994, 13, 505.

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98 J . Derek Woollins

condensation reaction of lead cyclophosphate was in~estigated.,~ An interesting spectroscopic study used boric acid trimethylester as a probe molecule in IR studies which enabled the Lewis base properties of MgO, CaO, ZrO,, TiO,, SnO,, and Sb,O, to be compared.58

Sulfur chemistry has advanced on a number of fronts. There was an interesting report on the synthesis of long-chain polysulfanes by the reaction of dialkoxysulfones (RO),S with thiol~.~ ' X-Ray and FT Raman studies were reported on [M,C1,]AsF6. The novel [ClS(Cl)SSCl) + and [ClSe(Cl)SeSeCl] + cations were obtained6' by insertion reactions upon [MCIJAsF,. Radical formation has been described6' from the reaction of S,06F, with S4N4 at s g , the species formed are thought to be [S3N2]+ ' and [S,]".

The solid state structure6' of S(NSiMe,), (which is isoelectronic with SO,) has been described; the ( E ) / ( Z ) configuration is preferred6, which is in contrast with previous gas-phase electron diffraction studies.

A number of metal complexes of sulfur-containing ligands were reported. Oxidation of Mo(S,)(S,CNEt,), with rn-chloroperbenzoic acid gave the corresponding S,O complex which is S,S' ~ o o r d i n a t e d . ~ ~ Cyclooctasulfur adducts of WCl,.thf and WCl, were also described.64 Insertion into M-SR bonds has been found to be a good route for the formation of MSSR complexes; the treatment of CpRu(PPh,)(CO)(SR) with RSphth (phth = phthalimido) giving C~RU(PP~,)(CO)(SSR)."~ The reactions of perfluorinated amines with sulfur compounds have also been investigated.66

The reaction of Me,SiNPPh, with SOCl,, SO,CI,, and SCl, gives [SO(Cl)NPPh,], [SO,(Cl)NPPh,], and [SClN(PPh,)]CI re~pectively;~~ from X-ray studies, all three compounds appear to contain S=N and P=N.67 Related to this work was the report on the structure and NMR properties of bis(5,5-dimethyl-2-thioxo-1,3,2-dioxaphos- phorinan-2-y1)disulfide and diselenide.68 An interesting observation was made in the organic reaction between the thiocarbonyl group of monothiomaleimide and dienes, namely that the C=S group appears to be a more reactive dienophile than electron-deficient C=C group^.^'

The impact of Group 16 chemistry in the materials area has been well illustrated. For example, PVC membrane solid state electrodes based on thioether have been shown to be highly selective for Ag' with low detection limits and short response A number of macrocyclic liquid crystals with functionalized thio-crown ethers have been

'' G. Kura and T. Ueno, Polyhedron, 1994,13, 3105. 5 8 C. Li, S. Fu, H. Zhang, and Q. Xin, J . Chem. SOC., Chem. Commun., 1994, 17. 5 9 R. Steudel and H. Schmidt, Chem. Ber., 1994, 127, 1219. 6o P. Bakshi, P. D. Boyle, T. S. Cameron, J. Passmore G. Schatte, and G. W. Sutherland, Inorq. Chem., 1994,

61 F. Mistry, F.G. Herring, A. Haas, and F. Aubke, J . Fluor. Chem., 1994,66, 147. 62 M. Herberhold, S. Gerstmann, B. Wrackmeyer, and H. Borrmann, 1. Chem. SOC., Dalton Trans., 1994,633. 6 3 M.A. Halcrow, J . C. Huffmann, and G. Christou, Inorg. Chem., 1994,33, 3639. 64 W. Baratt, F. Calderazzo and L. M. Daniels, Inorg. Chem., 1994, 33, 3842. 6 5 A. Shaver and P.Y. Plouffe, Inorg. Chem., 1994, 33, 4327. 66 N. R. Patel, R . L. Kirchmeier, and J. M. Shreeve, Inorg. Chem., 1994,33,4403. 6 7 H. Folkerts, D. Nusshar, F. Weller, K. Dehnicke, J . Magull, and W. Hiller,Z. Anorg. A&. Chem., 1994,620,

6 8 M. J. Potrzebowski, G. Grossmann, J. Blaszczyk, M. W. Wieczorek, J. Sieler, P. Knopik, and H. Komber,

69 Y. Tamaru, H. Sakata, M. Kimura, H. Harayama, H. Konishi, K . Fugami, and S. Tanaka, J . Chern. SOC.,

'O F. Teixidor, M. A. Flores, L. Escriche, C. Viiias, and J. Casabo, J . Chem. SOC., Chem. Commun., 1994,963.

33, 3849.

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Inorg. Chem., 1994, 33, 4688.

Chem. Commun., 1994, 2365.

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Oxygen, Sulfur, Selenium, and Tellurium 99

Figure 3 The X-ray s t r ~ c t u r e ’ ~ of one example of a low-coordinate zinc complex

de~cribed.~’ An exciting development was the synthesis of thiol derivatized nanopar- ticles (1-3nm) of gold from (AuC1,)-/NaBH, in the presence of an alkane th i01 .~~ Aqueous sotutions of Cd,f /thiols/sodium hexametaphosphate were also found to form CdS colloids upon ultrasound i r rad ia t i~n .~ ,

The chemical conversion of CdS films into Ag,S films, by dipping thin films of CdS into AgNO, was reported74.

There also continues to be interest in new molecular materials. In this regard the formation of caesium tetrathiafulvalene-thiolates represents a significant advance.75 These caesium salts may be subsequently alkylated to give substituted TTF systems, including a macrocycle which incorporates the TTF skeleton.

investigated the evidence for n-bonding in boron-thiolates. A number of thiolato derivatives of Li, Mg, and Zn were described, including a rare example77 of two-coordinate Li. Low coordinate chalcogenido complexes of zinc have also been reported by other workers78 (Figure 3), as well as a new group of complexes based on the Wurtzite f r ame~ork .~ ’ Other complexes prepared because of their potential electronic/magnetic properties include a range of maleonitrile systems,80 and tin

A number of other papers on thiolates were of interest. Thus, one

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A. J. Blake, D. W. Bruce, I .A . Fallis, S. Parsons, and M. Schroder, J . Chem. SOC., Chem. Commun., 1994, 2471. M. Brust, M. Walker, D. Bethell, D. J. Schiffrin, and R. Whyman, J . Chem. SOC., Chem. Commun., 1994,801. R.A. Hobson, P. Mulvaney, and F. Grieser, J . Chem. SOC., Chem. Commun., 1994, 823. C . D . Lokhande and K. M. Gadave, M a t e r . Chem. Phys., 1993, 36, 119. J . Becher, J. Lau, P. Leriche, P. Merk, and N. Svenstrup, J . Chem. SOC., Chem. Commun., 1994, 2715. R . Wehmschulte, K. Ruhlandtsenge, M. M. Olmstead, M. A. Petrie, and P. P. Power, J . Chem. SOC., Dalton Trans., 1994, 2113. J . J. Ellison and P. P . Power, lnorg. Chem., 1994, 33, 4231. M. Bochmann, G.C. Bwembya, R. Grinter, A.K. Powell, K. J. Webb, M. B. Hursthouse, K. M.A. Malik, and M. A. Mazid, lnorg. Chem., 1994, 33, 2290. D. H. Zen, M. J. Hampden-Smith, and E.N. Duesler, Inorg. Chem., 1994, 33, 5376. J. V. Rodrigues, I. C. Santos, V. Gama, R . T. Henriques, J. C. Waerenborgh, M. T. Duarte, and M. Almeida, J . Chem. SOC., Dalton Trans., 1994, 2655.

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100 J . Derek Woollins

chalcogenides have been studied by several groups. A stabilization of terminal sulfido- and selenido- complexes was supported by ligation of the tin by the benzotetraaza[ 141 annulene dianion.8 Bis(tripheny1tin) chalcogenides were studied as precursors to SnS and SnSe. The (Ph,Sn),E compounds (formed from Ph,SnCl and Na,E) when heated to ca. 300 “C lose Ph,Sn and Ph,E which are both volatile and thus the remaining solid is the binary sulfide or selenide.82

Another interesting reaction for tin was the treatment of tin powder with Me,SBr in diethyl ether which gives SnBr,(SMe,), with both cis and trans isomers in the unit cell.83 Much of the tin chemistry described above has also been applied to studies of germanium with thiolate complexes,84 terminal GeE systems* having been reported. Some related platinum complexes were also described.86 Lead trichalcogenide anions [Pb,SnE, -,I2- (E = Se, Te) have also been described.87 Indeed, heavier main group systems appear to be gaining in interest with studies reported88 of thiocyanate and selenocyanate coordination to Bi”’ as well as89 Pb” complexes of [Ph,PS,I2 - .

Transition metal complexes with sulfur-donor ligands also continue to be extensive- ly studied. A ‘tetranuclear’ Ag, system was stabilized by [ 18]aneS,O, c o o r d i n a t i ~ n . ~ ~ The role of [RhMn(CO),(dppm),] in S-H bond activation was investigated9’ and examples of five-coordinate Re”’ with Skionor ligands were de~cribed.~’ Several sulfur/selenium containing clusters of note were described. A new Mo-W-S cluster complex family [{(OC),M)xM’S,]2- (M = Mo or W; M’ = Mo, or W, x = 1,2) has been de~cribed.~, Electrochemical studies on sulfur bridged ‘incomplete’ cubane-type Mo”/W” were compared with the X-ray structures for four new complexes.94 Binuclear Fe-Fe and Fe-Ru systems have also been described.95 Other (biologically important?) iron-sulfur clusters reported have in~luded~~Cp~(PhRC,S,),Fe,S, and (C5Me5)3(Ph2C2S,)Fe,S5 as well as Fe,S,L,(RNC), system^.^' Large cop- per/chalcogenide clusters still continue to excite interest. The energetics for a range of Cu,,Se,(PH,), systems have been studied by ab initio calculation^.^^

Mixed Mo and Cu-W selenium clusters were obtained from the reactions of [PPh,],[WSe4] with, for example, C U C N . ~ ~ An extremely facile route to Rh, Tr, and

M.C. Kuchta and G. Parkin, J. Am. Chem. Soc., 1994, 116, 8372. 8 2 P. Boudjook, D. J. Seidler, S. R. Bahr, and G. J . McCarthy, Chem. Muter., 1994, 6, 2108. 8 3 N. Bricklebank, S. M. Godfrey, C. A. McAuliffe, and R.G. Pritchard, J. Chem. Soc., Chem. Commun., 1994,

84 B. Kersting and B. Krebs, lnorg. Chem., 1994, 33, 3886. 8s M.C. Kuchta and G. Parkin, J. Chem. SOC., Chem. Commun., 1994, 1351. R6 W. Baratta, P . S. Pregosin, A. Bacchi, and G. Pelizzi, Inorg. Chem., 1994, 33, 4494. ’’ M. Bjorgvinsson, H. P. A. Mercier, K. M. Mitchell, G. J . Schrobilgen, and G. Strohe, lnorg. Chem., 1994,32,

’’ A. Crispini, R. J. Errington, G. A. Fisher, F. J. Funke, N. C. Norman, A. G. Orpen, S. E. Stratford, and 0.

695.

6046.

Struve, J. Chem. Soc., Dalton Trans., 1994, 1327. K. H. Ebert, H. J. Breunig, C. Silvestru, I. Stefan, and I. Haiduc, lnorg. Chem., 1994, 33, 1695.

yo A . J . Blake, R. 0. Gould, C. Radek, and M. Schroder, J. Chem. Soc., Chem. Commun., 1994, 985. ” L.S. Wang, R. McDonald, and M. Cowie, lnorg. Chem., 1994, 33, 3735. ” T. Maina, A. Pecorale, A. Dolmessa, G. Bandoli, and U. Mazzi, J. Chem. Soc., Dalton Trans., 1994, 2431. y3 B. Zhuang, P. Yu, L. Huang, L. He, and J . Lu, Polyhedron, 1994, 13, 125. 94 T. Shibahara, M. Yamasaki, T. Watase, and A. Ichimura, lnorg. Chem., 1994, 33, 292. ” T. Mitsui, S. Inomata, and H. Ogino, lnorg. Chem., 1994, 33, 4934. y 6 S. Inomata, K. Hiyama, H. Tobita, and H. Ogino, Inorg. Chem., 1994, 33, 5337. ” C. Goh, J.A. Weigel, and R.H. Holm, lnorg. Chem., 1994, 33, 4861. ” S. Dehnen, A. Schaefer, D . Fense, and R. Ahlrichs, Angew. Chem., lnt . E d . Engl., 1994, 106, 786. 99 R.J . Salm and J.A. Ibers, lnorg. Chem., 1994, 33, 4216.

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Oxygen, Sulfur, Selenium, and Tellurium 101

Figure 4 The X-ray structure" uf(q,-C,Me,)Ru(p~RTeTeR)(pz-TeR)Ru(r,C,Me5) (R = Tol)

Ga cubane-like clusters of Se and Te was found to be the reaction"' of E(SiMe,), I E = Se, Te) with Cp*MCl,. Related to this was a study of the conversion of late transition metal sulfide complexes into metal-sulfur cubanes.'"

In selenium chemistry there was a report on an HPLC method for the quantification of organo-selenium molecules'02 as well as a report on the synthesislo3 and X-ray structure of Al,(Se03),~3H,0. An unusual reaction was the report that camphor enolate reacts with selenium in thf to give the corresponding diselenidelo4 although different products are obtained in the presence of MeI. Ozonolysis of olefinic phenyl selenides followed by reductive work-up yields phenylseleno aldehydes and ketones with retention of the Ph-Se-group.lo5

Fundamental studies in P-Se chemistry included the X-ray structure of P4S4106n and of P2S5106b as well as a NMR investigation into P,Se,-,S,I(n = 0,1,2).lo7

l o o S. Schulz, M. Andruh, T. Pape, T. Heinze, €1. W. Roesky, L. Haming, A. Kuhn, and R. Herbstirmer,

l o ' D.A. Dobbs and R.G. Bergmann, Inorg. Chem., 1994, 33, 5329. l o ' K . Gottfried, K. Kalcher, K. J. Irgolic, and R. J. Magee, Appl . Organornet. Chem., 1993, 7 , 433. l o 3 W. T. Harrison, G. D. Stucky, R. E. Morris, and A. K. Cheetham, Report, 1992, Order No. AD-A251283,

33pp. From Gov. Rep. Announce. Index (U .S . ) , 1992,92, Abstr. No. 252445. I o 4 T.G. Back, B. P. Dyck, and M. Parvez, J . Chem. Soc., Chem. Commun., 1994, 515.

D.L. J. Clive and M. H. D. Postema, J . Chem. SOC., Chem. Commun., 1994, 235. ( a ) R. Blachnik, P. Loennecke, and J. Nuss, Z. Anorg. Allg. Chem., 1994, 620, 160; (h) R. Blachnik, P. Loennecke, K. Boldt, and B. Engelen, Acta Crystallogr., Sect. C, Cryst Struct. Commun., 1994, 50, 659.

Organometallics, 1994, 13, 4004.

lo ' P. Loennecke, R. Blachnik, and B. W. Tattershall, Z. Anorg. Al lg . Chem., 1994, 620, 1115.

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102 J. Derek Woollins

Layered compounds KMP2Se6 (M = Sb, Bi) which represent complexes of [P2Se6]4- have been prepared and studied.lo8 A novel coordination mode about tellurium was reported'" for [Ph,PS,] - . P-N-Se systems were also reported, for example"' [SeCl(NPPh,),] + and 2,3-bis[2,4,6-tris(trifluoromethyl)phenyl]selenodiphos- phirane. ' ' New selenium- and tellurium-coordination compounds have included [Re,I,(CO),(Se),] ' ' [(C5Me,)Ru(p2-RTeTeR)(p,-TeR),Ru(C,Me,)] ' ' (Figure 4) and complexes of C,S,Se,-containing ligands.' l4

New low-dimensional quaternary compounds such as KCu,AsS,have been ob- tained from reactions in supercritical amine solvent,' l5 whilst solid state ,'Se NMR studies were reported on [M(Se4),l2- (M = Zn, Cd, Hg).'',

Binary Se-N compounds continue to be studied although they must be considered to be difficult systems. A new preparation' l 7 of Se,N, from SeO, and Me,SiNPMe, gave a different crystal modification to .the previously reported methods. IR spectra for binary Se-N compounds formed by the condensation of microwave discharge products were also reported; NSe and NSe, being readily characterized at low temperature,' ' both [N(SC1)2]+,'19 and [N(SeCl)2]f'20.121 were further studied.

An interesting acyclic122 N-P-Se anion, K[Ph,P(Se)NSiMe,], was obtained from the reaction of Ph,P(Se)N(SiMe,), with KOBu'. With iodine the anion forms (Me,SiN)Ph,PSeSePPh,(NSiMe,). Other ternary P-N-S and P-N-Se systems have been further studied. Density function calculations were used to investigate' 2 3 the bonding in P,S,N4 systems, whilst chalcogen substituted diazenes were reacted with zero-valent palladium and lead complexes to give' 24

M[PhEN(4-MeC6H,)CNNC(4MeC6H4)NEPh](PPh,) M = Pd, Pt; E = S , Se. The preparation of [Ph,P,N,S,R] - anions and their complexation' 2 5 and reaction

with electrophiles' 26 have been described. A ruthenium complex of [Ph4P,N,S2I2 - was also

Tellurium-containing chalcogen nitrides developed well in 1994. There were reports

lo' T. J. McCarthy and M.G. Kanatzidis, J. Chem. SOC., Chem. Cornmun., 1994, 1089. lo9 A. Silvestru, 1. Haiduc, K.H. Ebert, and H.J. Breunig, Inorg. Chem., 1994, 33, 1253. 'lo H. Folkerts, K. Dehnicke, J. Magull, H. Goesmann, and D. Fenske, Z. Anorg. Allg. Chem., 1994,620,1301. l 1 H. Voelker, U. Pieper, H. W. Roesky, and G. M. Sheldrick, 2. Naturforsch. Section B., 1994, 49, 255.

'12 A. Bacchi, W. Baratta, F. Calderazzo, F. Marchetti, and G. Pelizzi, Angew. Chem., Int. Ed. Engi., 1994,106,

' 1 3 H. Matsuzaka, T. Ogino, M. Nishio, M. Hidai, Y. Nishibayashi, and S. Uemura, J . Chem. SOC., Chem.

' l4 C. Faulmann, J. P. Legros, P. Cassoux, J. Cornelissen, L. Brossard, M. Inokuchi, and H. Tajima, J. Chem.

'15 J.E. Jerome, P.T. Wood, W.T. Pennington, and J. W. Kolts, Inorg. Chem., 1994, 33, 1733. '16 P. J. Barrie, R. J.H. Clark, R. Withnall, D.-Y. Chung, K.-W. Woo, and M. G. Kanatzidis, Inorg. Chem.,

206.

Cornmun., 1994, 223.

SOC., Dalton Trans., 1994, 249.

1994, 33, 1212. H. Folkerts, B. Neumuller, and K. Dehnicke, ZAAC, 1994, 620, 1011.

I t s L. Andrews and P. Hassanzadeh, J. Chem. SOC., Chem. Commun., 1994, 1523. ' I 9 M. Broschag, A. Schulz, and T.M. Klapotke, Chem. Ber., 1994, 127, 2187. lZo K.B. Borisenki, M. Broschag, I. Hargittai, T. M. Klapotke, D. Schroder, A. Schulz, H. Schwarz, I. C.

1 2 ' M. Broschag, T. M. Klapotke, A. Schulz, and P. S. White, Chem. Ber., 1994, 127, 2177. 1 2 2 T. Chivers, M. Parvez, and M.A. Seay, Inorg. Chem., 1994, 33, 2147. lZ3 H. Jacobsen, T. Ziegler, T. Chivers, and R. Vollmerhaus, Cand. J. Chem., 1994, 72, 1582. lZ4 T. Chivers, K. McGregor, and M. Parvez, Inorg. Chem., 1994, 33, 2364. lZ5 T. Chivers, M. Edwards, R.W. Hilts, M. Parvez, and R. Vollmerhaus, Inorg. Chem., 1994, 33, 1440. 126 T. Chivers, R.W. Hilts, M. Parvez, and R. Vollmerhaus, Inorg. Chem., 1994,33, 3459. 1 2 ' T. Chivers, R. M. Hilts, M. Parvez, D. Risticpetrovic, and K. Hoffman, J . Organomet. Chem., 1994,480, C4.

Tornieporthoetting, and P. S. White, J. Chem. SOC., Dalton Trans., 1994, 2705.

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Oxygen, Sulfur, Selenium, and Tellurium 103

b

Figure 5 The X-ray structure'33 of the [C,,Te,(C0,,J2- anion

on the preparation' 28 of Cl,Te,N,S and Cl,Br,Te,N,S and also [C1TeNSNSI2 '[Cl] [AsF,] which contains a five-membered TeN,S, ring.'29 The reaction of Ph,P(NSiMe,),Te(Cl)=NR (R = PPh,NSiMe,) with Bu'NHLi gives (Bu'NTeNR), which is a diimide dimer.' 30

A series of very weakly coordinated anions, M(OTeF,), (M = As, Sb, Bi), has been described.' 3 1 New gold 1 3 2 and cobalt133 tellurides have been reported. [AuTe,,14- was obtained by ethylenediamine extraction of KAuBiTe, alloy whilst [Co, 1Te,(C0),o]2- (Figure 5 ) was prepared from CO,(CO), and Na,Te,.

A. Haas and M. Pryka, J . Chem. SOC., Chem. Commun., 1994, 391. A. Haas, M. Pryka, and M. Schafers, Chem. Ber., 1994, 127, 1865.

I 3 O T. Chivers, X. Gao, and M. Parvez, J . Chem. SOC. , Chem. Commun., 1994, 2149. 1 3 ' H. P .A. Mercier, J.C.P. Sanders, and G. J . Schrobilgen, J . Am. Chem. SOC., 1994,116, 2921.

1 3 3 R . Seidel, R. Kliss, S. Weissgraber, and G. Henkel, J . Chem. SOC., Chem. Commun., 1994, 2791. S. S. Dhingra and R. C. Haushalter, Inorg. Chem., 1994, 33, 2735.

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104 J . Derek Woollins

A novel gallium t e l l ~ r i d e , ' ~ ~ [Ph,P]GaTe,(en),, held together by NH-Te hydro- gen bonds, has been obtained by cathodic dissolution of Ga,Te, in ethylene diamine/[PPh,]Br. A one-dimensional, telluride, C,,Zr,Te,,, was ~yn thes i zed '~~ at 900 "C from Zr and Cs,Te,/Te, this system contains numerous Te-Te interactions. A ternary zintl anion [Cu4SbTe,,13- was obtained'36 by solvent extraction upon KCuSbTe, alloy. The structure consists of a tetrahedral Cu+ coordinated to SbTe:- and Te; - ligands.

This report has described a few of my personal highlights in Group 16 chemistry. It is evident that O/S/Se/Te chemistry continues to contribute to inorganic, organic, and materials chemistry in many ways. The breadth of work makes Group 16 a fascinating and often surprising part of the periodic table and this is doubtless sure to be true in future years.

134 C. J . Warren, D. M. Ho, R. C. Haushalter, and A. B. Bocarsly, J. Chem. SOC., Chem. Commun., 1994. 361 1 3 ' J .A. Cody and J .A. Ibers, Inory. Chem., 1994, 33, 2713. 1 3 6 S. S. Dhingra and R.C. Haushalter, J . Am. Chem. SOC., 1994, 116, 3651.

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