aO OT Tetrahedron Trigonal bipyramid Octahedron Trigonal peism Pentagonal bipyramid Dodecahedron ‘Square antiprism Cube Hexagonal bipyramid Tricapped trigonal prism Monocapped antiprism Bicapped antiprism \ woo e Octadecahedron Icosahedron Cubsoctahedron AnticubeoctahedronTR, Feluer SUNDARG 5 Professor oA GHOSH, eho, Department of Tran Tatts of Henny n ute of Teehnolp Chennl gra nn, HetneparHffas Cluster Molecules’é the p-Block Elements Catherine E. Housecroft University Lecturer in Inorganic Chemistry, University of Cambridge OXFORD NEWYORK TOKYO (OXFORD UNIVERSITY PRESS. 1994ey Contents 1 Introduction and definitions ‘ 2 Clusters in the elemental state 4 3 Aspects of the structures of cluster compounds i 4 Bonding in clusters % 5 Synthetic routes to clusters 3 6 Reactivity of clusters "4 Index 92 Series sponsor: ZENECA ‘ZENECA is a major international company active in four main areas of business: Pharmaceuticals, Agrochemicals and Seeds, Specialty Chemicals, and Biological Products. ‘ZENECA’s skill and innovative ideas in organic chemistry and bioscience create products and services which improve the world’s health, nutrition, environment, and quality of life ZENECA Is committed to the support of education in chemistry.1 Introduction and definitions 1.1 The p-block elements The p-block elements are those lying in groups 13 to 18 of the periodic table. This text focuses attention on elements in groups 13 to 16. Each group 13 element possesses three valence electrons, each group 14 element, four, each group 15 element, five, and each group 16 element, six. These numbers are fundamental to an understanding of the chemistry of the p-block elements. 1.2 Whatis a cluster? In this book, a cluster is defined as a neutral or charged species in which Electron deficient: This s a term there is a polycyclic array of atoms (Fig. 1.1). The cluster may be homo- or thats used when the number of hnetero-atomic. It may be naked with no directly bonded peripheral atoms as {\jemone totiovicen Sette in elemental P, or the Zintl ion [Pbs}*. In other cases, the cluster may exhibit _ electron bending scheme. a central core. For example, [Bgl] consists of a central Be-unit in which a terminal hydrogen atom is attached to each boron atom. Edges of the cluster- core may be bridged by atoms (e.g. H) without total loss of a bonding interaction between the cluster atoms (¢.g. BgHj9). These differences may be rationalized in terms of bonding and will be discussed in later chapters. Many transition metal cluster compounds are known (e.g. Rhy(CO);2, Ose(CO)js, and (Fey(CO);3]?-) but these are beyond the scope of this book. JAN whl Sn a fr ADS, Ié | Ke V7 ONY SER fhe Fig. 1.1 Examples of clusters formed by p-block elements; structures of P4, [Pbs]*, [Bg], BgHo. and P4Og. Bonding descriptions for clusters vary depending upon the availability of valence electrons; methods of rationalizing the bonding in cluster molecules will be described in Chapter 4. Clusters involving boron atoms are often described as being electron deficient; such molecules possess an inadequate number of valence electrons to be held together by a network of localized 2- centre-2-electron bonds. On the other hand, a P, tetrahedron has enough valence electrons to allocate a localized 2-centre-2-clectron bond to each edge and there is still a lone pair left. over per phosphorus atom. It is important therefore to recognize that a line drawn between two-atoms in the2 Introduction A line drawn between two atoms In ‘a cluster does not necessarily imply the presence of a localized bond. ‘A deltahedron is a specitic type of polyhedron—one with all triangular faces. RGe<——> GoR Ger | RGe—|—> Ger Ger R= CH(SiMes)2 Fig. 1.2. Structure of GogiCH(SiMes)a}5. WA Fig. 1.3 The crown ring of Sg. gd Tetrahedron Trigonal Dipyramid Octahedron ——_Trigonal prism Fig. 1.4 Polyhedral cages for n= 4 106. cluster framework does not necessarily imply the presence op bond; in Pyand PiOg it does, but in (Pos) IBgHgP>, and Bac eg Some clusters are more open than others—compare Py and pM, 1.1 The terms clased and open clusters are used commonty by oF of these terms is not trivial because electron deficient clutys tian treated inthe same way as other species. Foran electron deicieg o closed cage corresponds to the parent deltahedron, e.g. the cage set (Beli) (Fg. 1.1) is an octahedron and is closed. The surface ee shows no deviation from tangular faces. 1a departure fom tiny is observed, e.g. in BgHo (Fig. 1.1), then the electron deficient Cluster j, described as being open. This concept is examined in Chapter 4.“ is Cluster molecules in which there is an adequate numberof electon form localized 2-centre-2-electron bonds between adjacent atoms aes” restricted to deltahedral structures but exhibit instead a wide range Polycyclic frameworks. Ges{CH(SiMes)a}g(Fig. 1.2) adopts a tite Prismatic structure and not an octahedral one, The trigonal prism iy ar open than the octahedron but for a species in which there are plenty bonding electrons available, it is a natural choice (see Chapter 4) soy describing Geg{CH(SiMe3)q}¢ a8 an open cluster could be misleading. At this stage, the reader should be aware that there is a descriptive problem. There comes a point when the threshold between a cluster nd.¢ ring is crossed. In elemental sulfur (Fig. 1.3, the eight atoms ae amangedia a single ring. Could such a ring be classed as an ‘open cluster? For Sg, this seems to be an unnecessary complication, In this book, the term ring will be reserved for monocyclic and bicyclic molecules. A cluster will be defined as a molecule Possessing at least a tricyclic structure. An exception is the borane BgHyo (Fig. 3.1). There is one large group of compounds that cannot fall into this definition—in gener, organic molecules containing fused rings cannot Tealistically be classed as clusters although some possible candidates are discussed in Section 3.5. 1.3. Polyhedral cages The structures of many of the clusters described in this book are based upon regular polyhedra. For electron-deficient clusters, these parent polyhedra exhibit triangular faces only, ie, they are deltahedra. The term parent polyhedron is used because many clusters possess incomplete polyhedral frameworks and such structures are most readily described in terms of being derived from a complete polyhedron by the removal of one or more vertices. This concept will be addressed in Chapter 4, The minimum number of atoms that can form a closed (three dimensional) cluster molecule is four. Throughout this book, the number of cluster vertices will be defined as n, For n = 4, the tetrahedron is the only closed polyhedron which may be adopted (Fig. 1.4). For n = 5, the trigonal bipyramid is usually observed (Fig. 1.4). For 1 = 6, atoms may be arranged in two triangles that are either mutually eclipsed or staggered to give the trigonal prism 0 octahedron, respectively (Figs, 1.4 and 1.5).Cluster molecules of the p-block elements 3 Some commonly encountered polyhedral cages are shown on the front Rotate inside cover of this book. The pentagonal bipyramid (n = 7), dodecahedron (n = 8), hexagonal bipyramid (n = 8), tricapped trigonal prism (n = 9), bicapped antiprism (x = 10), octadecahedron (n = 11), and icosahedron (n = 12) are all deltahedra, For n = 8, one structural possibility is the simple cube. ‘The square antiprism (related to the cube by rotating one pair of opposing square faces so that they are mutually staggered) is a structure that must also be considered for n = 8 since the energy barrier between the dodecahedron, the square antiprism and the hexagonal bipyramid is low. For n= 9, a second polyhedral option is the monocapped antiprism. This is related to the tricapped trigonal prism by breaking the bottom edge of the central prism of the tricapped trigonal prism and allowing the resultant 4-sided face to open ‘out into a square. This generates the monocapped square antiprism. For n = 12, the cubeoctahedron and anticubeoctahedron are accessible structures in roth Conversion of a tigonat addition to the icosahedron. prism to octahedron. ‘The polyhedra shown in Fig. 1.4 and on the inside book-cover constitute a at, restricted set, restricted because polyhedra with faces larger than a square are e not included. Examples of closed clusters of the p-block elements exhibiting pentagonal or hexagonal faces are not common but examples that are known are important: elemental boron and Cp will be discussed in Chapter 2. 1.4 Further reading Chapter 2 Wells, A-F. (1984). Structural Inorganic Chemistry, Sth Edn, OUP, Oxford. _Structures of the elements Kroto, H.W. (1992). Ceo: Buckminsterfullerene, The Celestial Sphere that The story of Cgp Fell to Earth, Angewandte Chemie, Int, Ed., Engl., 31, 111-129, Corbridge, D.E.C. (1974). The Structural Chemistry of Phosphorus, Elsevier, Phosphorus Amsterdam. Baudler, M. (1987). Polyphosphorus Compounds—New Results and Perspectives, Angewandte Chemie, Int. Ed., Engl., 26, 419-441. Greenwood, N.N. and Earnshaw, A. (1985). Chemistry of the Elements, Chapters 3-6 Pergamon Press, Oxford. Structure, bonding, synthesis, Greenwood, N.N. (1989). Boron Hydride Compounds. Chapter 2 in Rings, "4 Feactivity Clusters and Polymers of Main Group and Transition Elements (ed. HW. Roesky), Elsevier, Amsterdam. Housecroft, C.E. (1990). Boranes and Metalloboranes: Structure, Bonding and Reactivity, Ellis Horwood, Chichester. Kennedy, J.D. (1984, 1986), The Polyhedral Metallaboranes, Parts I and II. Progress in Inorganic Chemistry, 32, 519-679; 34, 211-434, Fort, R.C. and Schleyer, P. von R. (1964). Adamantanes: consequences of the Diamondoid Structure. Chemical Reviews, 64, 277-300, Haiduic, 1. and Sowerby, D.B. (1987). The Chemistry of Inorganic Homo- and Heterocycles, Vols. 1 and 2, Academic Press, New York. Wade, K. (1976). Structural and Bonding Patterns in Cluster Chemistry, Advances in Inorganic Chemistry and Radiochemistry, 18, 1-66. Mingos, D.M.P. and Wales, D.J. (1990). Introduction to Cluster Chemistry, Prentice Hall, New Jersey.‘The Octet Rule: An s- ot p-block ‘element obeys the octet rule if the nucleus is surrounded by eight valence electrons. e.g. In NHg, the formation of three N-H bonds introduces three electrons into the valence shell of the N atom and the N nucteus then has an octet of valence electrons. Fig.2.1 Opand Os. 2 Clusters in the elemental state 2.1. Which elements form discrete clusters in their elemental states? In this chapter, the occurrence of clusters for members of the p-block in their elemental states is described. Distinctions are made between elements which do not form clusters at all, elements for which cluster units form part of an extended lattice, and elements which exhibit discrete (i.e. separated) clusters in at least one allotrope. ‘All the inert (noble) gases (group 18) are monatomic; this is a consequence of the complete electronic configuration exhibited ‘by cach element. The members of group 17, the halogens, are all diatomic molecules. The general ground state valence configuration of a halogen atom X is ns? np® and therefore a single bond to another halogen atom to form X provides ‘an octet of valence electrons around each atom, i.e. the octet rule is satisfied (Eqn 2.1). Ha ag pe Eat aera te Ret Eqn 24 In group 16, the ground state valence electronic configuration of an element E is ns? np*. This permits the formation of two covalent bonds. In compounds of sulfur and heavier elements in group 16, an expansion of the valency to four or six may be possible by the use of low lying d-orbitals if they are available. There are three ways in which an atom E may satisfy the octet rule in the elemental state: (i) by the formation of a diatomic molecule containing an E=E double bond (Figs. 2.1 and 2.2), (ji) by the formation of a cyclic molecule (Fig. 2.2), or (iii) by the formation of a polymeric chain of atoms (Fig. 2.2). In the clemental state at standard temperature and pressure, oxygen alone in the group favours diatomic molecule formation. The triatomic molecule, ozone, (Fig. 2.1), is thermodynamically unstable with respect to O> (Eqn 2.2). The experimental O-O distances in Qs indicate some degree of interaction between the terminal oxygen atoms of the V-shaped molecule. 3 (9) —> %,02(9) AG? =-163.2 1 mot Eqn22Cluster molecules of the p-black elements 5 Polymer E ; NE Ring Fig. 2.2 Molecule formation in the elemental state for a group 16 element, E. Rings could theoretically be of any size. cE=e Diatomie Dimensional itice mlonis aN ec | SE e ee Tether Fig. 2.3 Structural choices in the elemental state for a group 15 element, E. In group 15, the ground state valence electronic configuration of ns? np? allows an atom to form three covalent bonds. In compounds of phosphorus and its heavier congeners, participation of low lying d-orbitals may allow an expansion of the valency from three to five. In its native state, an atom of the first element of group 15, nitrogen, satisfies the octet rule by forming a triple bond to another nitrogen atom. The N=N bond is very strong (945 kJ mol!) and the formation of diatomic N, is very favourable. For elements lower in the group, the formation of a tetrahedral cluster in the elemental state is observed, although the molecule E, occurs with varying degrees of stability depending on E (see Sections 2.3 and 2.4), Three-dimensional lattices are the alternative possibility; for example, a network of puckered six-membered rings is observed for black phosphorus and related structures are exhibited by a-arsenic, c-antimony, and a-bismuth, The reader is directed to references given in Section 1.4 for further details of three-dimensional arrays,6 Clusters in the elemental state Buckminsterfullerene Diamond i, in each layer of graphite are involved in x- Fig. 2.4 Structural diversity in the elemental state of carbon. The carbon ators in each lay Boning giving s-delocalizaton throughout he layer. The layers of fused hexagons In graphite are staggered and altemate ‘an @-b-a pattem. More detailed diagrams of buckminsterfullerene are given in Fig. 2.7. The characteristic ground state valence electronic configuration of a group 14 element is ns? np?, In the absence of d-orbital participation four covalent bonds may be formed per atom. The allotropic forms of carbon are diamond, graphite, and the recently discovered fullerenes (Fig. 2.4). Of these, only the fullerenes are discrete clusters and will be discussed in Section 2.2; Csg (buckminsterfullerene) is shown schematically in Fig. 2.4. Silicon and germanium both crystallize with a diamond-type lattice. Tin and lead are metallic, Solid lead possesses a close-packed structure. The low temperature form of tin (grey or atin) exhibits the diamond structure but at 13.2°C lattice distortion occurs to form white B-tin in which each tin atom has six nearest neighbours. B, In group 13, the ground state valence configuration of ns? ns! would ZL | Nn permit the formation of three covalent bonds but such implied simplicity of aa B BS, structure is not observed in the elemental state. The metallic character of 7 ViVi \ aluminium and its heavier congeners leads to close-packed lattices for these x hk X A elements, The atoms of elemental boron tend to aggregate in an effort to LALA LM, overcome the problem of each atom possessing an empty 2p atomic orbital B—— BF were it only to form three covalent bonds, This phenomenon is also seen at a NX | L molecular level in its compounds (see Chapters 3 and 4). In the elemental 8 state, the clusters which form as a result of atomic aggregation are not Fig.2.6 Anlcosahedral Byz-custer discrete although the icosahedral By,-cluster (Fig. 2.5) is a recurrent which Is a recurrent structural unit structural building block, in allotropes of boron,Cluster molecules of the p-block elements 7 @ ® Fig.2.6 The construction ofthe Burt in rhombohedral boron: (a) the contral BygYeosahedron, (b) the attachment of 12 terminal boron atoms to the central B2-icosahedron, (c) the incorporation of each terminal boron atom into a pentagonal pyramidal unt (ony 6 of tho 12 are shown for clarity), () the network of 12 Isolated pentagons arising from the 12 pentagonal Pyramids, (e) the Bo-cage formed by jiring together the 12 pentagons, Note the direct relationship between the outer Bgo~ ‘cage and buckminsterfullerer8 Clusters in the elemental state ‘The name fullerene has been coined after the architect Buckminster Fuller who is well known for his geodesic domes. boron to be described was the cr-tetragonal form ated as a carbide or nitride, BsyC2 oF BsgNp, The resent as a result of synthetic conditions. In the rapelusters are arranged in an approximately close-packed lattice. Boron-boron interactions between the icosahedral Clusters are weaker than those within a By2-unit. The structure of f. rhombohedral boron is complex and consists of Bgq-units connected by Big. units and single boron atoms. ‘There are 105 atoms in the unit cell and the formula Bigs may be usefully written as (By)(B10-B-Bio). The Byy-cage is ing it up from the icosahedral cluster which lies at its idered by building i Se ae inal boron atom is bonded to each atom of the By- centre (Fig, 2.6a). A termi ocd luster (Fig, 2.6b). Each of the 12 terminal atoms is incorporated (as the pical atom) into a pentagonal pyramid of boron atoms. Six of these pentagonal pyramids are shown in Fig. 2.6c, There are twelve pentagonal pyramids in the complete 3-dimensional cage and the network of twelve pentagons thereby produced is shown in Fig. 2.6. When joined together, these pentagons form an approximately spherical Bgo-cage (Fig. 2.6¢) identical to that of Co (Figs. 2.4 and 2.7). Figure 2.6 illustrates that the Bg4- cage of Bthombohedral boron may be represented as (B2)(B12)(Bea). “After considering the elements of the p-block, it is clear that only a few elements exhibit discrete cluster units in their native state. These are detailed below. The first polymorph o but this has been reformu carbon or nitrogen content is pr Gethombohedral allotrope, B 2.2 Fullerenes ‘The characterization of Cop and C7 The emergence of the chemistry of the carbon cluster Cgo, buckminster- fullerene, has occurred since 1985, and dramatically so since a method for producing bulk quantities of Cg and C79 was developed in 1990. Fig. 2.7 The structures of (a) Cog and (b) C7o. A simpler ropresentation of gg is shown in (c).Cluster molecules of the p-block elements 9 Pure graphitic soot (which contains a few per cent by wei cea is produced by evaporating pronit rods in an snoapers ot Relies a a pressure of about 100 torr and condensing the vapour. Upon dispersal in benzene, some of the condensed product dissolves to give a red solution from which a black crystalline material is obtained, The dominant components of this material are Cgg and Crp (Fig. 2.7); a mass spectrum shows a strong peak at 720 a.m.u. and a less intense peak at 840 a.m,u. corresponding to Cég and Cho respectively. Evidence is available for higher fullerenes such as Cy4 but data concerning these molecles are, as yet, sparse. : Magenta Cand red Cp may be separated chromatographically by using hexane, The initial characterization of Czy and Cp relied heavily upon spectroscopic methods. For Cp, the infrared spectrum exhibits four absorptions at 1429, 1183, 577, and 527 cm; this pattern is in accordance with the number of vibrational modes predicted for a cage with icosahedral (iy) symmetry. Raman spectroscopic data are consistent with this result, In 1990, X-ray diffraction studies on platelets of Co (i.e. not a single crystal diffraction study) indicated that the solid consisted of an ordered array of spheroidal molecules, each =7 A in diameter and separated from its neighbour by =3 A. The !'C NMR spectrum of Ceo shows a single resonance at 8 143 indicating that all 60 carbon atoms are in equivalent sites; the chemical shift compares quite well with that observed for benzene at 5 128. ‘The results of an electron diffraction study of gaseous Cy (in 1991) provided An important feature of he Cen evidence for the structure shown in Fig. 2,7a. All atoms are equivalent but ig consucted from hexagonal and there are two distinct types of bond: those between hexagonal faces (aCg-Cg _ pentagonal faces; the pentagons bond) and those at the junction of one hexagonal and one pentagonal face (a af Isolated from one another. C5-Cs bond). Distances in the gas phase are 1.40 A and 1.46 A respectively and may be designated as double C=C and single CC bonds. In mid-1992, the single crystal structure of Cog was reported and confirms the structure shown in Fig. 2.7a; interatomic distances are about 0.01 A shorter than those obtained from the gas phase study. Fig.2.8 Schematic representation ofthe "6 NMA spectrum of Cro. <— 48 100 140 190 ‘The structure of Cyp has yet to be determined by a single-crystal X-ray diffraction study although the cage shown in Fig. 2.7b is consistent with spectroscopic data and is the same as the cage crystallographically confirmed in the derivative (n?-C7o)Ir(CO)CI(PPh;)2. The molecular structure of C7p may be derived from that of Ceo by splitting the latter into two hemispherical-C3o units and rejoining them after the insertion of a band of ten carbon atoms. A molecule of C7o possesses Ds, symmetry and the appearance of five resonances (intensity ratio 1:2:1:2:1) in the "SC NMR spectrum (Fig. 2.8) indicates that the molecule is not fluxional in benzene solution on the NMR spectroscopic timescale. Two-dimensional '°C-!9C NMR spectroscopy permits the correlation of a "C NMR spectral signal due to one nucleus with one or more signals arising from one or more carbon10 Clusters in the elemental state Fig. 2.9 {'BuCeq}a. LU/lig. NHs /"BUOH Cen, a Cocos No, $ a Ne cl ° Eqn 24 ‘The reduction potentials in Eqn 2.5 are measured with respect toa standard calomel electrode. nucle to which the first atom is bonded. In this way, the connectivities of the | noms may be deduced and results are in agreement with the structure shown OE has been determined by bomb thalpy of combustion of Coo has by bom calsenn ie-2 700.8 ki mol! and this gives a value of AM/((cryst) = +2,280.2 5.6 kJ mol"! ‘The reactivity of Cgo and C7o ved the greater attention. The atoms in OF Gai, er agar dest See bonds. Coois highly reactive towards radical species and has been termed a radical-sponge. In the reaction between Cgp and PhCH" up to 15 radicals add to the cluster. Alkyl radicals, R°, add rapidly to Ceo. For R= 'Bu, the ESR spectroscopic signal assigned to ‘BuCo oe as the temperature of a benzene solution of the species in raised from 300) 10 350 K. The process is reversible and these data suggest that the radical formed is in equilibrium with a dimeric species (Eqn 2.3). The structure proposed for the dimer {'BuCeo)2 is given in Fig. 2.9. The stability of (RCeo}2 depends upon the steric requirements of R. 2 (BuO gy? "BUC gp~Ceo'BU Eqn23 The reactivity of a Cgp molecule does not reflect that of benzene even though the surface of the cluster is reminiscent of connected benzene rings. Cap teacts with nucleophiles and the polyfunctional nature of the Cgo cluster is a source of non-selective product formation. One method of controlling the number of ‘butyl or ethyl substituents introduced into the cluster is to titrate ‘BuLi or EtMgBr against Ceo. After protonation, the monoalkylated derivatives CeoFBu and CgoHEt are produced, respectively. Further reaction can occur to give more highly substituted products. Ceo undergoes Birch reduction (Eqn 2.4) to give a mixture of isomers of CegH36. Reoxidation with the quinone shown in Eqn 2.4 regenerates the Ceg cluster. The reduction potentials for the stepwise reduction of Cgy and Cyp are given in Eqn 2.5. Significantly, the first and second reduction steps for the two clusters are very similar but it is easier to reduce [Cyg]* than [C¢o]2- to the corresponding trianion. ~o12 mv 1000 mv ~1482 mv Co == Car = | =—— cal 616 mV 988 mV 1404 mv aed & == GF SS I SS Expansion (or the so-called inflation) of the Cgo cluster occurs during reaction with diphenyldiazomethane (Fig, 2.10). The structure of the product has been confirmed in an X-ray diffraction study of Cqi(CgHy-4-Br)>. The carbon-carbon distance at the point in the fullerene at which the diphenylmethylene fragment has added is 1.84 A. This indicates that expansion from a Ceo to Cg, cage has indeed occurred,Cluster molecules of the p-block elements 11 Fig. 2.10 Expansion or inflation of the Cgo cluster. “the preferential reactivity of a Cg~Ce bond in Cgy has been observed in several reactions with transition metal complexes (Fig. 2.11). Recall that in Ce double bond characteris associated with the C;-Ce edges. Cey displaces ethene from (PhsP)2Pt(n?-C2H4). Related to (PhsP),Pt(?-Céo) is — Modes of attachment of an alkene to {(ELP):Pt)¢(Caa) in which six PtL, (L = phosphine) units are bound to six amelal atom. separate Cs-Cg junctions. Both Cgy and Czy exhibit alkene-like character in Hy Hp addition reactions with (PhsP)aLr(CO)CI to give (n-Cep)ir(CO)CKPPh;), and © = (n®-Cya)Ie(CO)CIPPhs)2 respectively. In each product, the two carbon atoms II? Mtn | Mn that are directly bonded to the transition metal atom are pulled out from the & fullerene cluster towards the metal atom. a, awe wy (PhgP)alr(CO)C 1, Excess 0:0, 2. Excess 4-R-CsH,N (R=Hor'Bu) R Wore Fig. 2.11 Selected reactions of Coo with transition metal complexes; all products have been charactorized by X-ray ceystallography.12 Clusters in the elemental state 60" Pa J Bs 221A ' ar Fig. 2.12 Molecular P4. ‘The osmylation of Cgp in the presence of a pyridine base (Fig. 2.11) gives an adduct Cgg030s(0),(NCsHl4-4-R)2 (R = H or tbutyl). In the case of R = ‘Bu, the loss of m-character from the Cs-Cz bond which interacts with the osmium fragment is confirmed by an increase in carbon-carbon bond length from 1.45 A in Ceg to 1.62 A in Ceo0208(0),(NCsHs'Bu)a- ‘The cavity within a fullerene cluster may be occupied by a metal atom of an appropriate size. The laser vaporization of graphite impregnated with L105 leads to LaCeg and ESR spectroscopic data indicate that the compound should be formulated as (La**][Cgo?-]. A fullerene with a metal atom, M, within the cluster is called an endohedral metallafullerene and is designated as M@C,, Members of this series include fullerene hosts other than Coy, e.g, Seg@Cpp, Se3@Cep, U@Cop, K@Cu4, and Cs@Cas- Doping Coo with potassium or rubidium produces K3Ceo or RbsCeo. These species are metallic at room temperature but become superconducting at 955°C and -245°C respectively. By comparison with other superconducting. materials, alkali metal doped Ceo exhibits a high onset temperature of superconductivity and this property has evoked tremendous interest in * fullerene chemistry as a whole. Geometrical parameters are from a {gas phase electron diffraction study. 7 oF oP So Fig 2.13 2.3 White phosphorus, P4. Structural and thermodynamic considerations White phosphorus is a metastable state and forms upon condensation of phosphorus vapour, Crystalline white phosphorus exhibits two structural modifications. Below -77°C, the hexagonal f-form is present and above this temperature, the cubic @-form exists. Both the a- and B-forms consist of discrete P, molecules (Fig. 2.12) which persist when white phosphorus melts (-228.9°C) and vaporizes (7.5°C). Above 554°C, P, dissociates into diatomic P2; the dissociation energy for the process Py —> 2 P2 is 217 KI mol. The dissolution of white phosphorus in non-aqueous solvents such as CS>, PCls, or liquid ammonia also occurs with retention of the Ps molecules. P, is insoluble in water; itis stored in water to prevent oxidation (Fig. 2.13). Excess - p Oe JIN Controted [0] oT No _—— —— rg 1 PSP fr oP ers? Pyrolysis 200-400°C ina sealed tube ee Pg + PQ, (n=7, 8, 0F9)Cluster molecules of the p-block elements 13 Reactivity of Py White phosphorus is soft and inflammable, In air, it spontaneously oxidi to Pi0jo (commonly referred to as phosphorus pentoxide, "P06" although witha limited supply of oxygen P4O, is formed, At high temperautes P,O, gisproportionates to P, and higher oxides (Fig, 2.13), White Phosphorus does pot react with water, but does react with aqueous alkali to yield the ypophosphite anion (Eqn 2.6). ‘Tho structures of phosphorus ‘vides and related compounds are discussed in Section 3.8. See Soction 4.3 fora discussion of the bonding in P4, P4Og, and P4040. P, ol J, storesno te |! \ + 4H Po | 42h Eqn26 pelor uo H Pp Re p “ZS +4RLUi+4RBr ——~ 2 \ p, tHUBr + 2 Pye Eqn 2.7 CIS . SIS a R P R=2,4,6-'BusCgHs PAZ ‘The,Pestetrahedron opens up eff te P, butterfly configuration. to'a butterfly" Conformation:whensitris In2.7. The internal dihedral angle of the fituents are arranged in an exo,exo- BP, + 12LIPH, ——> 6LijPig + 8PHy Eqn 28 ‘The compound Li,P;¢ is formed when white phosphorus is treated with LiPH, (Eqn 2.8); LisP; is also produced. A change in the ratio of reactants in Eqn 2.8 may lead to the formation of LisP, and LisPag in place of LizPg. Like [P,.]*-, (Fig. 2.14), the anions [P2;]>- and [P2.]* have structures which ae related to an allotrope of the element, Hittorf"s (monoclinic) phosphorus ig. 2.15). 1P NMR spectroscopic data suggest that discrete [Pye], [Pa], and [P2¢]* anions exist in solutions of LigPis, LisP2,, and LigP 6, respectively. Each 2-coordinate phosphorus atom formally bears one negative charge. Fig, 2.14 Structure of the dianion [Py]. Ina butterfly or similar cluster, exo- and endo-substituents are defined as follows: endo14 Clusters in the elemental state a £ —| / oF i i“, L \. i h f \I thi) Netti LAINIE} IPN AN ANE | @ ® P. P ” ~ P. Pp aa A OR RR OR SAAN A ‘4 ch Leen PALI PRL PRA LAIN ENN IU» Fig.2.45 Structures of (a) Se: i . r IPs (0) Peal and (c) Hitt (o) (monoclinic) phosphorus. The eighteen electron rule ‘The eighteen electron rule is an extension of the octet rule as applied to transition metals. In a low oxidation state, a transig metal will accept electrons from ligands so that the number of valence electrons (ve) surrounding the metal is 18. 2.9. Ni(0) has a ground state electronic configuration of 4s 3d ® (10 ve) and requires eight more electrons from surrou ligands. .. It forms compounds such as Ni(CO), in which there are four 2-electron donor ligands. Since each phosphorus atom in P, carries a lone pair of electrons, the cluster can function as a Lewis base. In Fig. 2.16a, the coordination of one phosphorus donor from P, to the nickel atom results in the nitrogen donor of the (Ph;PCH,CH;);N ligand breaking free from the coordination sphere. This allows the metal atom to obey the 18 electron rule both in the starting material and in the product. Reaction of P, with (PhsP)3RhCl gives (Ph;P),RhCl(n?-P,) in which two phosphorus atoms of the P, ligand interact with the metal atom (Fig. 2.16b). The starting complex contains a 16 electron thodium(I) centre, but the product obeys the eighteen electron rule. Not all reactions of white phosphorus with transition metal complexes Refer to Section 4.5 fora detntion 84 t© simple coordination products. The reactions shown in Fig. 2.17 an illustrate a range of observed pathways. Disruption of the tetrahedral Py cluster occurs, in the simplest case through the substitution of a phosphorus atom for an isolobal transition metal fragment such as {Cp*Cr(CO)s} or {Co(CO),}. Stepwise substitution may occur as is observed in the reaction of P, with Cox(CO)g. This yields Co(CO)3P3, Co,(CO)_P2, and Co3(CO)4P each of which has a tetrahedral cluster core. Reorganization of the phosphorus atoms may occur to generate cyclic ligands of the type 73-P3, n!-Py, 1°-Ps. and 1)°-Ps. The reaction of P, with Cp*Ti(CO), gives Cp*;Ti,P, (Fig. 2.17) the structure of which may be described as a cubane. -Cluster molecules of the p-block elements 15 EY. Ay ae N—N + —— | PSP P Phy (a) Ph i P cl—Rh—PPhg + JIN ee - eo > | Pape Pro ©) Fig.2.16 Coordination modes of P, in (a) NIIN(CHaCHaPPh)a)(o-Pa) and (b)trans-Ah(PPhs)zClin?-P4)- or Cm NO Go, P AS, LN iY p— opncon aes [Cp'Fe(CO)sb . Pole i op’ P ae [Cp'CHCO lle ee Le N, weno, 0% TANG ZAIN oe K™ rE Se ory Ce oo - WY + /| | N Ni &. Ppa or Fig.2.17 Reactions of white P with pentamethylcyclopentadienyl (Cp*) carbonyl derivatives of selected transition metals. 2.4 Arsenic, antimony, and bismuth In the vapour phase, arsenic exists as tetrahedral As molecules. Raman spectroscopic data for the matrix isolated species confirm tetrahedral (T) symmetry. At relatively low temperatures, antimony vapour consists mainly of Sb, molecules, Matrix isolation experiments have confirmed the nature of this species and results indicate the presence of Sbz and Sbs in addition to Sb, Similarly, electronic spectral data for Bi, in solid neon or argon matrices have shown that Bi, molecules are present along with Biz diatomics. The inaccessibility of Ass, Sbs, and Bi, as room temperature species precludes their use as synthetic precursors. At room temperature and pressure, arsenic, antimony, and bismuth possess structures that are related to the network of uckered six-membered rings observed for black phosphorus.exo: This term is applied to an atom Cluster molecules and ions cor or group attached by a localized 2- contre-2-electron bond ina terminal OF an empirical formula are the site outside the cluster core. endo: This terms applied to an atom or molecular fragment which bridges an edge or caps a face of the cluster core; the electrons from the atom or fragment are involved in cluster bonding. Classification of borane clusters with representat Single cage closo [BpHrl Single cage ido BrHned Single cage arachno BHns Single cage hypho BrHnis Cages coupled by a common B atom ByH4g = (BsHe)(B2Hs) Cages coupled by an exo-B-B bond {nidole {8Hnsal n=5,10 Cages coupled by an exo-B-B bond {arachno}z {BpHnesle n=4 Cages coupled by a shared B-B edge ByoHig. BigHto, BraHta, B1aHzo, BreH20, Bratza Cages coupled via Bs-faces Bootie Nomenclature for borane clusters ‘The name should reveal the number of boron atoms, the number of hydrogen atoms, and the charge. The number of bot atoms is given by a Greek prefix except for the use of Latin nona- (nine) and undeca- (eleven). The number of hydrog atoms appears as an Arabic numeral after the written name. For an ion, the charge is given at the end of the name. Sti the class of cluster should also be included. Byotye = (BsHal2 3 Aspects of the structures of cluster compounds 3.1 Boron Neutral boranes and hydroborate dianions ntaining boron constitute the largest group of ‘block element. The simplest clusters in terms boranes and borane anions (hydroborates). A borane is a compound which contains only boron and hydrogen; it is also known as a boron hydride. Compounds fall into series according to formula ‘and whether or not the cluster is a single cage or consists of two or more coupled cages. All cages are based upon triangular faced polyhedra; these nd some other polyhedra incorporating square faces are drawn on the front inside book-cover. clusters exhibited by a single p-l members of each class tetraborane(10) arachno-tetraborane(10) pentaborane(9) nido-pentaborane(9) pentaborane(11) arachno-pentaborane(11) hexaborane(10) nido-hexaborane(10) hexahydrohexaborate(2-) hexahydro-closo-hexaborate(2-) decaborane(14) nido-decaborane(14) 1,1" of 1,2'- or 2,2decaborane(16) conjuncto-1,1'- or 1,2 or 2,2'-decaborane(16)Cluster molecules of the p-block elements 17 poived fom the osteo: ys ay és A Dd Hl HHH H H ag cos a Bato arachno: pov rom the pentagons! bpyrai: H Ay nH H HOH BHE so Peto BH, Not crystallographically a aractno characterized, Derived from the dodecahedron: ‘i H Hl H 4 2 4 BH Bete BHie ae arachno Detved fom the tcapped tigona prism: K a Leon AX : N (BH Byte oso ido “The cago is more open than might be expected; B--— Bare folong {0 bo bonding interactions each Hoe =8H, HN =bildgingHaton Fig. 3.1. Structures of closo-hydroborate dianions and nido- and arachno-boranes possessing single cages.18 Aspects of the structures of cluster compounds Derived from the bleapped square antiprism: [ByoH rol closo Derived from the octadecahedron: H H. H HOH H\ { H H Y H Hi [BH BioHia Bs closo nido arachno Confirmed structurally for [By Hio(SMea) Derived from the icosahedron: ZISy ZISs Bit closo @=2H =e =BH, = =H = bridging Haton Fig. 3.1 (continued) Structures of claso-hydroborate dianions and nido- and arachno-boranes possessing single cages.Cluster molecules of the p-block elements 19 tures of the closo-hydroborate dianion ne sms f the clasehrdrboratsdanions and neta ido nd. Thea aon an arachino-boran real eGo he dianions (B,H,]>- exhibits f@¢hno are derived from the Latin Srgosed (cl0s0) oe ge. Compounds of type B,Hyy4 and ByH,,, loWs{or cage (Grock xaos), open structures, the former being related tothe closed deliahedron by Lath nds fornost, and Greek 88 j poses Or one vertex (nido-cluster) and the ler related by the removal SY. apaxim for web, rspoctvey. vortices (arachno-cluster). In cach of the [ByH,]*, B,Hy,4, and See Section 4.6 for details of tho gervaive clUtersy CVETY boron atom carries one terminal hydrogen atom, — ‘latlonships betwoen the classes. For a boron atom of low connectivity in a cluster of type ByHayg. (wo Foal iyérogen atoms may be attached. Clusters consisting of two or more fared cages are called conjuncta-boranes ‘ofthe borane clusters consisting of coupled cages, those which are Coupled borane cages ao called coupled via 2 localized 2-centre-2-electron exo-B-B bond are readily _ Conjuncto-clustrs. caved in terms ofthe constituent single clusters, (BsEp) is derived from va efly clusters, with a B-B bond replacing one terminal B-H bond on win cluster. Since each BsHy cluster possesses two types of boron atom, x. The paucity of carbon-rich carbaboranes (x >)) may be understood if one remembers that a {CH)-unit replaces a (BH}-- ot (BH)-unit, Thus, beginning with a closo-hydroborate dianion, it only takes the introduction of two carbon vertices to render the cluster neutral. Cationic’ clusters are rare in group 13 or 14, Starting from a nido-borane B,Hy,4 it is Possible to introduce up to four carbon atoms without affecting the overallCluster molecules of the p-block elements 21 molecular charge. The structure of one of the t related t0 BgHj2, and C;Me4B,H) is related to carbaboranes with a relatively high carbon co: basis of known nido- and arachno-boranes, clusters of this type is small, Zs, ZS, Zs ZS i SO@ 1 Wo isomers of CyMe4D Hy is DgHig, Even though a range of ‘ontent may be formulated on the in practice the number of known (xy 1,2-C,BioHi2 1,7-CByoHye AA2-C.Bigthe Fig. 3.6 Numbering scheme for the icosahedron, and the three isomers of closo-C8gHya. | Isoelectronic species When two or more molecules, ions, or molecular fragments possess the same number of valence and core electrons, they are said to be Isoelectronic. This term is, however, often used to refer to species which simply possess the same number of valence electrons. ‘with respect to the number of valence electrons available, the folowing fragments are isoelectronic wth each other: {BHY-, {CH}, {CMe}, (NH}*, (AIMe)~, (SIEX) ‘The following tetrahedral clusters possess the same number of valence electrons within the cluster and are regarded as being isoelectronic with each other: 4, AS¢, Big, Sd4, SigHa(hypothetical), Cy'Bug Heteroboranes ‘The substitution into boranes of cluster units isoelectronic with {BH}-may be extended to fragments other than (CH). As will be described in Chapter 4, itis the number of available valence electrons possessed by a fragment which controls its ability to mimic a monoborane vertex in a cluster. Thus the CH-for-(BH)- replacement may be extended to CR and SiR (R = alkyl or ary)), Similarly, a Sn or Pb atom that bears an exo-lone pair of electrons may replace a neutral {BH}-unit, and an (NH)-unit or an S atom may replace a {BH)?-unit. This is no different from replacing a {CH}-unit in an alkane by an {NH} or {O} to generate a secondary amine or ether, respectively. Main-group fragment substitutions of this type lead to a wide range of heteroborane clusters and examples are shown in Fig. 3.7. The incorporation of an (AIMe) fragment in place of a (BH) vertex in {B);H),]*- is shown in Fig. 3.7. Likewise, AIBgH,, is structurally related to Grachno-BsH,,, The incorporation of a (GaR} or (Ink) fragment into a borane or carbaborane cluster gives rise to gallaboranes, gallacarbaboranes, indaboranes, or indacarbaboranes such as 2-GaB3Hjo (Fig. 3.8), 1-Me-1-E- 2,3-CoB 4H, (E = Ga or In, Fig. 3.7) or 1-Et-1-Ga-2,3-CyBoH}1. A naked22 Aspects of the structures of cluster compounds thallium atom is present in (3-TI-1,2-C>ByHj,]~ although the rather long T1. B (range 2.66 A to 2.74 A) and TI-C distances (2.91 A and 2.92 A) suggest that a better formulation is as the ion-pair (TI]* (1,2-CsBol,]>. Sn. ri JAA K\ Ny ON" 8 H H e.g. =H; SiMes 1-81-2,9-Re-2,9-CoB iH 4-Me-1-In-2,3-C,8.He 1-SB5Hy . Related to [8,H,]~ Related to [ByHrl™ Related to [ByHy0] Me Pa A La aS Wyy yt ie BH NBysHie 1,2-Mer-1,2-SisBiotho [AMeB yy Hal Related to [ByzH ia) Related to [ByaHyal~ Related to [ByaHral™ Fig. 3.7 Selected heteroborane clusters. The structurally related borane or hydroborate dianion is given. / Incorporation of silicon atoms into borane clusters has the scope to Med eed atan hchede the that provide a range of compounds related to carbaboranes since {SiR} = {CR}. Poistortusorottwe-clustars which Despite this theoretical prospect, only a few such compounds are known, €.. ‘share a common atom. 1,2-Mey-Si2B oHi2 Fig. 3.7) and commo-3,3'-(3-Si-1,2-CByH1)2 Fig. 3.9). € 's— H H Hac Mie Soa AES ces | ah a X< p< | H Fig. 3.9 Silicon atom fusing together two C89. 7 Fig. 3.8 2-GaB3Hjo, an anal ing together two CzBg-clusters in commo,3-(3-Si arbi. oo (C2BgH4)2; 880 Fig. 2.8 for the numbering scheme In the icosahedron.Cluster molecules ofthe p-block elements 23 ers of boron other than the polyhedral boranes the boron hides BsCly ByCly, and ByClp exhibit closed detahedral By cores (Fig. 3.10). BgBrg is isostructural with ByCly, Other members of this Fes are B,Cly for = 10-12, ByBry for n = 7-10, Byly for n = 8 and 9, as, il as several coupled clusters, e.g. (ByBrg}2. No fluoride derivatives are cust well Seni wn, Iti signfiant that these molecules are neutral and yet possess closed cage structures. The dianions [B,X,J]> (n = 6, 9; X=Cl, Br, ) and [B.XaP- (t= 10, 12; X-= Cl, Br) also exhibit closed deltaedralB,-custer vere This contrasts with the boron hydrides where closo-species are Served for dianions (B,H,]* and neutral analogues are not known. On the ‘ther hand, the neutral By'Bug cluster is stable and a closed tetrahedral cage mralogous to that in B,Cly has been crystallographically confirmed, The mean B-B distances in B,Cl, and B,y'Bu, are equal (1.71 A). Classical structures (structures with 2-centre-2-electron bonds) are not sully associated with boranes or carbaboranes but there are occasions when ‘classical structure is favoured. The tendency for a boron atom to participate jn cluster formation arises from a need to use its three valence electrons as tifectively as possible. If a n-electron donor is present, the formation of a deltahedral cluster skeleton may not be necessary. This is the case in C.H1B«(N'Pr.)s Fig. 3.11). The lone pair of electrons on each nitrogen atom is donated into the empty 2p orbital on the adjacent boron atom. Remember that a boron atom has fewer valence electrons than valence orbitals. Fig.3.10 Structures of B4Cl, (tetrah« Although a large group of compounds exhibiting boron-nitrogen rings exists, related cluster systems are not well represented. The same is true for B-P, B-As, B-O, B-S, and B-Se systems. Both the diamond-type (cubic) and hexagonal forms of boron nitride, (BN), possess lattice structures. From the former, it is clear that an adamantane-type unit is feasible for a combination of boron and nitrogen atoms but it is not exploited at the molecular level. An adamantane-like structure is observed for the anion [B,S;o}*- (Fig, 3.12) and has been structurally characterized for the Jead(Il) salt; each boron atom is 4-coordinate. A cubane-like cluster with two open edges is observed for [MeNBCly], ig. 313), Related to this is BuPB(CI)CH2B (CDPB), in which the open B.--B edges (see Figs. 3.13 and 5.10) of the cubane-like BuPa-core are bridged by methylene groups. 1edron), Belg (dodecahedron), and ByCl (ticapped trigonal prism). ‘The adamantane structure is defined in Fig. 3.19. Tho term cubane Is used to describe a molecule that exhibits a cublc-core of atoms. The archetypal molecule is Cel24 Aspects of the structures of cluster compounds Me i Sie, 8. Me. Yl \ v8 pe cB —|— <7 . = Ny Is Na ong MS PrN NPrp Fig. 3.11. Classical bicyclic Fig. 3.12 [848401 Fig. 3.13 [MeNBCr,, structure of CHaB4(N'Pro)4. Compare this to C2B4He in Fig. 35. 3.2. Aluminium Although aluminium is below boron in the periodic table, it does not fom many clusters that are analogous to boranes. The dianion [Aly,'Buy2)*is a rare example of a cluster in which all the core atoms are aluminium atoms and it illustrates the potential for aluminium to behave like boron in deltahedral cluster; [Al,2'Buj2]* possesses an icosahedral cage like BH). [RAIN], [RAINRT, R=H R=Et ReH R= "Pr e =ALR Unmarked vertex = N-R’ | Fig. 9.14 Structures of some iminoalane clusters, [RAINF', The Lewis acidity of an AIR; (R = H, alkyl, or aryl) group allows the | formation of adducts with Lewis bases. This general reactivity extends (0 cluster formation between {RAI} and (NR'} fragments. The degree of | oligomerization depends upon the synthetic conditions and on the steric requirements of the exo-substituents. Examples of tetrameric, hexameric, heptameric, and octameric iminoalane clusters are shown in Fig. 3.14 and in | each case, each aluminium and nitrogen atom is 4-coordinate forming one exo-bond and three skeletal interactions. The tetramer forms a cubic cage (cubane) and the hexamer is a hexagonal prism. The heptamer and octamer | i EteCluster molecules of the p-block elements 25 regular polyhedra lke the smaller clusters, the ‘ 7 or § are constructed of fused AlNz~ and Autor the ee posphacubane (RAIPR'J, (R='Bu and R'= SiPhy) has a hharacterized and is similar to the iminoalane cubane shown in xo not fort = alumina sqrvcturally © ig 3.14. Fas inclusion of (ERa)-units (E = Al or N) causes deviation from a closed cage strcture; the presence of two terminal substituents restricts the sercipaion ofthe ERs-nit in cage bonding, The stuctres of the clusters MAINIPr),(HAINH(Pr)3, (CIAD4(NMe),(NMe;),, and. (MeAINMe),- Hi {MeyAINEMe): are shown in Fig. 3.15. te 'PrHN’ | T > h00 wT Tan, i 4 "PHN Men AIH X=NPr@=AlH X=NMe2,@ = AICI X=NMe, @=AlMe Structures of (HAIN'Pr)a(HpAINH'Pr)g, the adamantane-like (see Section 3.5) (CIAI)4(NMe)a(NMea)4, and In general, ER, groups are sited along open edges of the cage; an exception is observed for two 'NMe groups in (CIAI}4(NMe}a(NMea),. Fig. 3.15 (WeAINMe)g(MepAINHMe)2. 3.3. Gallium and indium ‘The number of p-block clusters involving gallium or indium atoms is limited. (MeGaNMe),(MeGaNHMe), is isostructural with its aluminium counterpart Gig. 3.15) but analogues of the iminoalanes shown in Fig. 3.14 are not (as yet) known, The anions [GagS,o]8-, [Ga4Se1o]*, [InsS io], and [IngSejo]* are isostructural with [B4Sio]*- (Fig. 3.12). The same structural unit is observed in EjpSy6(SPh),] for E = Ga or In (Fig. 3.16). In forming these extended adamantane-like structures, the thiolate-sulfides of the group 13 elements parallel the behaviour of the d'® metals zinc and cadmium, for example in [ZnyoS4(SPh),6]* or [Cdy7Sq(SPh)29]*- The relationship follows from ‘the relative positions of Zn, Cd, Ga, and In in the periodic table; zine() is isoelectronic with gallium(II1), and cadmium({I) is isoelectronic with indium(IQ). 34° Thallium A usual feature of a thallium atom in substituent. This may be attributed to t ‘toms are incorporated into deltahedral [T1Sng}*- (see Section 3.7). ‘a cluster is the lack of a terminal the inert pair effect. Naked thallium 1 Zintl ions such as [TISng}*- and26 Aspects of the structures of cluster compounds Fig. 3.16 (InjoSj6(SPh)4\, Inert pair effect ‘The two s-electrons of a heavy p-block element may remain as non-valence electrons. This leads to a change in the characteristic oxidation state from nto (n-2) for the element. €.g. TI (group 13) shows a tendency to exhibit oxidation state +1 whereas Al (higher in the same group) exhibits oxidation sq 3. x x Boe, i x mosiZ i: x ee we de 7 x x X= OMe X=N'Bu X=N'Bu e@ =thalliumaton | Fig. 3.17 Structures of Tl4(OMe)4, Tla(MeSi)(N'Bu),, and Tig(MeSi)p(N'Bu)g, § In a series of thallium containing clusters, thallium acts as a Lewis acid. X\ The cube is the structural motif in Tl,(OMe)4, Tl(MeSi),(N'Bu),, and - s Tle(MeSi),(N'Bu),,(Fig. 3.17). In Tl4(OMe), and Th(MeSi),(N'Bu),, each Ss. thallium atom is 3-coordinate. In Tlg(MeSi),(N'Bu),, the double-cubane structure is supported by a short TI-TI edge of length 3.16 A. This is | considered to be a bonding interaction; the average intra-cube Tl-—Tl 5 a is 3.54 A. Cubane-residues are also apparent in Tls(S'Bu), (Fig. y 18). Os \s oS 3.5 Carbon The number of organic molecules with fused-cyclic carbon skeletons is vast =; S=S'y and will not be explored here save for a few relatively small molecules, the structures of which are related to those observed for cluster molecules of | Fig.3.18 Tig(S'Bu)g. other p-block elements, |Cluster molecules of the p-block elements 27 ‘Adamantane, CypHy5, (Fig. 3.19) is a tricyclic molecule and the structure resembles a portion of the diamond lattice (Fig, 2.4). There are two carbon sites: in one site the carbon atom is 3-coordinate within the cage and has one terminal substituent and in the second site the carbon atom is 2-coordinate ‘within the cage and has two terminal substituents, Each carbon atom is in a tetrahedral environment, Adamantane-like clusters occur regularly within the p-block and the differentiation between the two cage sites not only permits the incorporation of {ER}- and (ERp}-units but also allows the involvement of atoms with different numbers of available valence electrons (Fig. 3.19). More complex cages with recognizable adamantane units are diadamantane (congressane), triadamantane, and tetraadamantane (Fig. 3.20). Collectively these are examples of diamondoid hydrocarbons, 4 c. nc] ote N 07 ~o | f* I = (/ > lo I HO~| N N PLP ony er 0 uc 8h, Ly/ @ pee Fig.3.19 Structure of adamantane, CigHig, and three compounds with the adamantane cage: hexamethylene triamine (1,3,5,7-etrazatrioyclo[3.3.1.1°.7|decane), thiaadamantane, and phosphorus(ll) oxide, P4Og. Note that group 15 atoms replace (aro isoelectronic with) (CH) units and group 16 atoms replace (are isoelectronic with) {CHa}units. 2 & Ee & Fig.3.20 Structures of the diamondoid hydrocarbons adamantane, diadamantane, triadamantane, and tetraadamantane. ‘The antiisomer of tetraadamantane is shown, In the diamondoid cages, each carbon atom is 4-coordinate and tetrahedrally sited, In cubane, CgHg, (Fig. 3.21) and its derivatives, each 4- coordinate atom appears to be in a strained environment since the intra-cube C-C-C bond angles are fixed at 90°. The carbon atom can tolerate this structural constraint and, moreover, can accommodate further strain as evidenced in small ring systems such as cyclopropane and in a tetrahedrane cluster, both of which have C-C-C bond angles of 60°, The tetrahedral cluster requires bulky substituents for stability and crystallographic Confirmation of the structure comes from a study of C,'Buy. The CC bond distances of 1.48 A compare with a typical C-C single bond length of 1.54 - Note that, although not isoelectronic with one another, C,'Bu, and BaBuy C= eo &re isostructural. The B,-core is significantly larger than the C,-core with a DuLi ar Ooh Mean B-B distance of 1.71 A. eciuctes listance of 1.71 A. cage structures. Fig.3.21 Cubano