Structural Aspect of Platinum Coordination

Compounds: Part VI. Heteroborane Platinum

Derivatives
Clive E. Holloway
Department of Chemistry, York University, 4700 Keele St., North York, M3J1P3. Ontario, Canada.
and
Milan Melnik
Department of Inorganic Chemistry, Slovak Technical University, SC 81237,
Bratislava, Slovak Republic.

0. ABBREVIATIONS
cod cyclooctadiene PEt 3 triethylphosphine

dppe bis(diphenylphosphino)ethane Ph phenyl

dppb bis(diphenylphosphino)butane PMe 3 trimethylphosphine

Et ethyl P(Me) 2 Ph dimethylphenylphosphine

m monoclinic P(Ph) 3 triphenylphosphine

methyl tmnda N,N,N',N'-tetramethylnaphthalene-l,8-diamine

Me
or orthorhombic tr triclinic

1. INTRODUCTION

Platinum is a valuable and useful metal, and the chemistry of its compounds has been extensively
investigated. The relationship between structure and chemistry is of major importance for applications ranging
from industrial catalysis to biochemical activity. The kinetic inertness of Pt(Il) complexes has led to their
extensive use in investigations of geometric isomerism and reaction mechanism. A large number of structures are
known for platinum coordination compounds, around two thousand five hundred, and many of these have already

been correlated in our recent reviews /1-5Λ

There are a series of platinum heteroboranes, and these are the subject of this review, including one
hundred published structures analysed and classified in order to assist in understanding the stereochemical
interactions in the coordination sphere of platinum. The structures have been classified according to the nuclearity
(monomer, dimer, trimer), and are further subdivided within each set according to the coordination number of the
platinum atom. The compounds have been listed and referenced in the order of increasing coordination number,
increasing complexity of the coordination sphere and increasing atomic number of the principal coordinating
atom of the ligand.

2. MONOMERIC COMPOUNDS

2.1 Coordination Numbers Four and Five

Crystallographic and structural data for over thirty platinum heteroboranes, four-coordinate (4) and five-
coordinate (30), are collected in Table 1. Note that some authors include coordination Pt-B/C distances of over
240 pm, which we consider to be rather too long for a substantial σ-bond,

73
Vol. 29, No. 2, 2006 Structural Aspect of Platinum Coordination Compounds:
Part VI. Heteroborane Platinum Derivatives

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 Vol. 29, No. 2, 2006 Structural Aspect of Platinum Coordination Compounds:
Part VI. Heteroborane Platinum Derivatives

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79
Vol. 29, No. 2, 2006 Structural Aspect of Platinum Coordination Compounds;
Part VI. Heteroborane Platinum Derivatives

There are four derivatives in which one homobidentate borane chelates to platinum via two C atoms, with two ,
PMe 2 Ph 161, PPh 3 ΠI or PMe 3 /8/ ligands completing a distorted square planar geometry about the Pt(II) atom.
The P-Pt-P bond angles range from 91.5(2)° to 94.3(1)°, and the C-Pt-C bond angles range from 94.8(3)° to
107.2(3)°. The mean Pt-P bond length increases with increasing size of the respective ligands in the order:
227.7(4) pm ( P M e 2 P h ) , 231.0(2) pm (PPh 3 ). The mean Pt-C bond distance of 216.5(10) pm is 12.3 pm shorter
than the Pt-P mean value, as expected.

Thirty five-coordinate derivatives /9-32/ have a terdentate borane ligand, homodentate with three Β atoms /9-
30/, heterodentate with two Β atoms and a S atom /31,32/. The remaining two coordination sites are occupied by
P-donors, one being a homobidentate chelate /12/ and the others being pairs of monodentate ligands to create a
PtB 3 P 2 /9-30/ or PtB 2 P 2 S /31,32/ inner coordination sphere.
It is well known that two limiting stereochemistries may be distinguished for five-coordination, a square
pyramid (coordination 4+1) and a trigonal bipyramid (3+2). In the platinum boranes neither of these appear to be
involved, with the Β atoms on one side of the platinum centre and the two Ρ atoms on the other side. The
structure of Ρΐ(η 2 ^ρρβΧη 3 -Β 3 Η 7 ) /12/ is shown in Figure 1 as an example. The triborane unit resides
symmetrically disposed with respect to the dppe-Pt moiety, with the Β atoms within bonding distance of the
metal atom. The internal dihedral angle of the PtB 3 butterfly arrangement is 133.4°. The central Β atom is closer
to the Pt atom (211.9(12) pm) than the other two (217.3(12) and 216.0(3) pm). The dppe--Pt moiety is
unexceptional, the methylene groups of the dppe chain being arranged above and below the PtB 3 plane. The P-Pt-
P bite angle is 85.3(1)°.

Fig. h Structure of Ρί(η2-άρρε)(η3-Β3Η7) [12

80
Holloway and Melnik Main Group Metal Chemistry

The B-Pt-B bite angles range from 44.6° to 51.0° (ave. 47.5°). The mean Pt-P bond distances increase in the
order: 228 pm (PEt3) < 229 pm (PMe2Ph) < 231 pm (PPh3), which follows the increasing size of the respective
ligands. The mean Pt-P bond distances for the homobidentate P-donor ligands are 228 pm (dppe) < 232 pm
(dppb). The former creates a five-membered and the latter a seven-membered metallocycie with mean P-Pt-P bite
angles of 85.0° and 94.8°, respectively.
The boranes themselves can be classified into five structural and stoichiometrical groups which are: closo-
boranes; nido-boranes; arachno-boranes; hippho-boranes and conjuncto-boranes. In the series of monomeric
platinum heteroboranes with four- and five-coordination only three of these groups are found; closo- /6,8-
10,13,17,24,25,29/, nido- /7,11,20-23,27,28,30/ and arachno-boranes /9,12,14,15,18,19,26,31,32/.
There are four examples where two crystallographically independent molecules differ mostly by degree of
distortion /ll,13,25,29/. The coexistence of two or more species like these is typical of the general class of
distortion isomerism /33/.

2.2 Coordination Number Six

There are seventeen coloured derivatives in which the Pt(II) atom is six-coordinate, and their crystallographic
and structural data are summarised in Table 2. 'ITiirteen yellow derivatives /34-40a/ have a homo-tetradentate
borane plus two P-donor ligands to give the PtB 4 P 2 chromophore. The structure of bright yellow Pt(PMe3)2(r|4-
C 2 B 6 H 2 ) 734/ is shown in Figure 2 as an example. The compound exhibits C2 molecular symmetry, having a

81
 Vol. 29, No. 2, 2006 Structural Aspect of Platinum Coordination Compounds:
Part VI. Heteroborane Platinum Derivatives

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Part VI. Heteroborane Platinum Derivatives
Structural Aspect of Platinum Coordination Compounds:
Holloway and Melnik Main Group Metal Chemistry

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85
Vol. 29, No. 2, 2006 Structural Aspect of Platinum Coordination Compounds:
Part VI. Heteroborane Platinum Derivatives

closo-polyhedral cage with geometry approximating a tricapped trigonal prism, whose low connectivity "cap"
positions are occupied by the three heteroatoms.
Three orange/red derivatives /40-42/ have the PtB4SP chromophore. In the first /40b/ a nido-7-
platinaundecaborane has an exopolyhedral Ν,Ν-diethyldithiocarbamate ligand bridging the Pt and B(2) atoms to
give a five-membered ring (PtBSCS). The tetrahapto Pt to borane bonding has a considerable twist distortion
relative to other examples of this type without the metallocycle feature. The B-Pt-B bite angle is 90.1(2)°. The red
cluster /41/ has a nido-eleven-vertex {PtB10} polyhedral skeleton and a five-membered (PtSCOB) ring of
exopolyhedral cyclisation via one thiobenzoate unit. The Pt atom is bound to the thiobenzoate S atom, the PPh3 Ρ
atom and four Β atoms of the {PtB10} cage. The orange red cluster /42/ has a similar inner coordination sphere
about the Pt atom. The B-Pt-S bite angles are 79.8(8)° /41/ and 80.4(8)° /42/.
The structure of yellow Pt(PMe2P)2^ 4 -C 2 B 9 H in -l-Ph) /36/ shows that the borane coordinates to the Pt(II)
atom via three Β atoms and one C atom. Two PMe2Ph ligands complete an inner coordination sphere about the Pt
atom (PtB3P2C).
The data in Table 2 give a mean Pt-P bond distance increasing in the order: 231.5 pm (PMe 2 Ph) < 232 pm
(PEt 3 ) < 234 pm (PPh3) < 235.5 pm (PMe3); with an average value of 2.33 pm. It can be seen that the mean Pt-B
bond distance of 225 pm, for boranes coordinating with four Β atoms, is about 3 pm longer than those where one
Β atom is also bonded to an S /40/ or Ο /41/ atom of a bridging ligand. The mean B-Pt-B bite angle is 42.8°.
Finally, the borane ligands are found in closo- /34/ and nido- 735-42/ polyhedral cages.

2.3 Coordination Number Seven

The crystallographic and structural data for ten coloured derivatives with a seven-coordinated Pt atom are
summarised in Table 3. The structure of a red complex /43/ is shown in Figure 3, a complex of a macropolyhedral
16-vertex rf-hexadecacarboranyl based on the structure of a conjuncto-borane. The borane consists of a nido-
{PtB7} cluster and a nido-{PtB )0 } cluster conjoined with a Pt-B vector as the common edge.

F i g . 3 . S t r u c t u r e of P t ( P M e 2 P h ^ 6 - B i 6 H i 8 P M e 2 P h ) [43]

86
Holloway arid Melnik Main Group Metal Chemistry

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Vol. 29, No. 2, 2006 Structural Aspect of Platinum Coordination Compounds:
Part VI. Heteroborane Platinum Derivatives

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Holloway and Melnik Main Group Metal Chemistry

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89
 Vol. 29, No. 2, 2006 Structural Aspect of Platinum Coordination Compounds:
Part VI. Heteroborane Platinum Derivatives

The structure of a yellow cluster /45/ is based on a PtB10P icosahedron with the Pt and Ρ atoms occupying
adjacent positions. The compound appears to derive from the capping of the five-membered open face of the
eleven-vertex nido-7-phospoaundecaborane cluster with the metal centre. The inner coordination sphere about the
Pt(II) atom is PtB4P3.
There are four derivatives of composition Pt(PR3)2(Ty5-ZBIf)Hu)), where R is PMe2Ph and Ζ is S /46/, or PEt3
and Se /19/, PPh3 and Se /47/ or PEt3 and Te /48Λ All belong to the closo class. Crystals of the clusters exhibit
conformational polymorphism and fluxional behaviour of the Pt(PR3)2 units in the closo-twelve-atom
metallaheteroboranes with the PtZBio cage. The overall cage structure is a distorted dodecahedron in which the
Pt(PR3)2 unit is bonded to a ZB4 ring. The conformation of the PtP2 unit over the ZB4 face is essentially the same
in each of the compounds /19,46-48/, and may be rationalised by consideration of the highest occupied and
lowest unoccupied molecular Orbitals (HOMO-LUMO) interactions between the Pt(PR3)2 and ZB I0 H I0 units/19/.
The inner coordination sphere about each Pt(II) atom is PtB4P2Z, with Ζ defined as above.
A red derivative /49/ has a closo PtAs2B9 geometry giving a distorted icosahedron with the Pt and two As
atoms forming one triangular face. The Pt(II) atom is surrounded by three B, two Ρ and two As atoms.
There are two derivatives, purple and orange /40a/ both having Pt(PEt3XSePh) moieties with the Pt atoms
pentahapto coordinated by nido-7-CB10 cage frameworks. The cage of the purple compound incorporates another
SePh group attached to a Β atom in a site with respect to the {CBBBB} ring ligating the Pt atom. This is also the
case for the incorporated 0(CH2)4C1 substituent in the orange derivative. Each Pt(II) atom adopts a PtB4CPSe
chromophore.
The molecular structure of Pt(PEt3)2(H)(Ti4-SB9H,o) /50/ has a Pt atom completing an eleven-atom icosahedral
fragment and bonded to S, three B, and two Ρ atoms together with a hydride ligand (PtB3P2HS).
The data in table 3 show platinum hexahapto coordinated by a conjuncto type of heteroborane /43,44/, and
pentahapto coordinated by closo /19,45-49/ and nido /40a,50/ types of heteroborane. The mean Pt-B and Pt-Z
distances for the pentahapto heteroboranes lengthen with increasing covalent radius of the Ζ atom in the order:
222 and 23.5 pm (C, 77 pm) < 233 and 266 pm (S, 102 pm) <227.5 and 267.5 pm (Se, 116 pm) < 228 and 270.5
pm (Te, 136 pm). The mean Pt-P bond distance increases in the order: 230.5 pm (PMe2Ph) < 233.5 pm (PEt3) <
234.0 pm (PPh3).
There are three-membered metallocycles formed and the effect of both electronic and steric hindrance of the
coordinating atom can be seen in the opening of the L-Pt-L bond angles. These angles open in the order: 46.5°
(C,B) < 47.8° (B,B) < 48.0° (B,S) < 51.7° (B, Se) < 52.5° (B,P) < 54.0° (B,As) < 56.5° (B,Te) < 57.5° (As,As).

2.4. Coordination Number Eight (Sandwich)

There are seventeen derivatives with an eight-coordinate Pi atom in a sandwich environment, and these are
listed in Table 4. The crystal structure of a golden yellow derivative /51/ reveals well separated [PhCH2NMe3J+
cations and [Ρΐ(η4-Β10Η12)2]"2 anions. The latter resides on a crystallographic inversion centre, slightly but
significantly distorted from C2h point symmetry due to crystal packing. Molecular geometry calculations suggest
that the {B i0 H 12 } ligand does not fit particularly well with either a nido-{BluH12}"2 or an arachno-{B1()H12}'4
formalism. The Pt atom is sandwiched by two {η4-Β,0Η12} cage fragments (PtB8).

90
Holloway and Melnik Main Group Metal Chemistry

Two orange derivatives 1521 are shown in Figure 4. One contains a [Pt(a«i/-n4-B18H?il)2]"2 and the other a
[Pt(syH-T|4-B18H2o)2]'2 anion. Each of the isomeric anions can be viewed as two nineteen-vertex subclusters
(PtB^Ha)) joined via the common Pt vertex. In each case the subcluster itself can be viewed as a nido-
platinundecaboranyl and a nido-decaboranyl unit fused by one B-B edge in common. The nido-
4
platinadecaboranyl description implies a η Pt-borane bonding mode.

Fig. 4. (a) Structure of [Pt(anti-n4.Bi8H2o)2]'2

(b) Structure of [Pt(syn-ti4.Bi8H2o)2]"2 [52]
91
Vol. 29, No. 2, 2006 Structural Aspect of Platinum Coordination Compounds:
Part VI. Heteroborane Platinum Derivatives

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93
 Vol. 29, No. 2, 2006 Structural Aspect of Platinum Coordination Compounds:
Part VI. Heteroborane Platinum Derivatives

A golden yellow derivative /53/ contains ppn+ cations and [Ρί(η 4 -(0 5 Η,,)B10H,o>2]"2 anions. The complex is
composed of two decaborane cages, each bonded in a η4 fashion to the Pt atom, which is a common vertex in two
11-vertex cages. Consistent with the nido-electron count of each cage, the cage frameworks are based on an
icosahedron missing one vertex. The Pt atom sits on a crystallographic centre of symmetry, and the two cages are
symmetry related.
The structure of a blue-red cluster /54/ consists of a nido-eleven-vertex {PtB m } subcluster fused, with a
{PtB2} triangular face in common, to another such moiety which is itself fused to a nido-ten-vertex {BU1}
subcluster, with a {B2} edge in common. The Pt atom is, surprisingly, not in an open face site.
In a yellow cluster 1551 the Pt atom is coordinated on one side by the open {CBBBB} pentagonal face of the
nido-7-CB in H,i cage, and on the other side by a CI atom and two PPh2Ph molecules.
There are three pale yellow derivatives 156,511 in which r|4-cyclooctadiene with a r|4-heteroborane form a
sandwich about the Pt centre with an inner coordination sphere of PtC6B2. Another two red-orange derivatives
/58/ have a pair of heteroboranes in refashion, forming a staggered sandwich configuration about each Pt atom
(PtGfB4).
An inner coordination sphere of PtB4C2P2 is found in four derivatives /59,60/. A if-carborane-metal bonding
is seen with a remarkable flexing of the 10-vertex Tf-{C2B8H9X} moiety between extreme nido and arachno 10-
vertex geometries. Two PX3 (X = Me2Ph 1591 or OMe /60/) complete the inner coordination sphere about the Pt
atoms.
The open face of the nido-CB 10 H u cage in a colourless derivative 761/ is pentahapto (B4C) coordinated to the
Pt atom. Two PEt3 ligands with a hydrido ligand complete the coordination about the Pt(II) atom (PtB4P2HC). In
another derivative /62/, a Pt(IV) atom is coordinated in a symmetrical sandwich between two planar pentagonal
fragments (C2B3) of the σ-carbonyl anions, with a dihedral angle of 173°.

3. DI- and TRIMERIC COMPOUNDS

There are sixteen coloured dimeric platinum heteroboranes, for which the relevant data are shown in Table 5.
The structure of a yellow dimer /63/ consists of a four-vertex Pt2B2 and an eight-vertex Pt2B6 subcluster conjoined
at a common Pt-Pt edge, as shown in Figure 5. There is an essentially linear P-Pt-Pt-L axis to which the B6 and B2
subclusters are appended: P(l)-Pt(l)-Pt(2) 174.8(1)°, P(2)-Pt(2)-Pt(l) 178.3(1)°. The Pt(II)-Pt(II) bond distance of
262.1(1)° is the shortest found in the heteroborane platinum chemistry.
In another yellow dimer /64/ there is also an essentially linear P-Pt-Pt-P axis ίο which two equivalent B s
subclusters are appended: P-Pt-Pt' and P'-Pt'-P 175.5(1)°. The Pt(II)-Pt(II) bond distance of 264.4(1) pm is
somewhat longer than in the previous case /63/. The cage of a yellow dimer /8/ is related to a nido icosahedral
geometry, having a substantially flatter open face. The second Pt atom lies outside the polyhedral framework and
is involved in a 3-centre interaction with Β (Pt-B 208(3) pm) and another Pt atom (Pt-Pt 282.0(2) pm. In another
yellow dimer /66/, the twelve-vertex closo-diplatinadodecaborane is seen to be based on a closed {Pt2B10}
icosahedron, with the metal atoms adjacent to a nido or "slipped" closo geometry. The interplatinum distance of
286.3(2) pm suggests reasonable strong bonding.

94
Holloway and Melnik Main Group Metal Chemistry

Fig. 5. S t r u c t u r e of Pt2(PMe2Ph)2(n3-B2H5)(n3-B6H9) [63]

The basic {Pt 2 B I6 } cluster of a dark orange example /67/ consists of a closo twelve-vertex {l,2-Pt 2 B| 0 } unit
and a nido nine-vertex {2,3-Pt 2 B 6 } unit, conjoined with the closed triangular Pt 2 B faces in common. The Pt-Pt
distance is 291.2(4) pm. The molecule of another dimer /10/ has a cage which can be described as a tricapped
trigonal prism in which the metal atoms vector is a capping linkage. The Pt-Pt distance is rather long (302.98(10)
pm), but lies roughly perpendicular to the two sets of P 2 Pt planes.
In the red dimer /8/ the Pt 2 C 2 B 5 cage has the geometry of a highly distorted trigonal prism, tricapped with two
C atoms and one Β atom. The Pt-Pt distance is 305.1(4) pm. The structure of a yellow dimer /68/ consists of a
nine-vertex n-arachno framework, obtained by removal of two adjacent vertices of connectivity (six and four,
respectively) from an eleven-vertex closo octahedron. The {(dppe)Pt} moieties are located at the 6 and 8
positions in the n-arachno B 9 H 15 framework, each replacing a BH group and a bridging Η atom.
In another red dimer /40a/ two TePh groups bridge the Pt(l) and Pt(2) atoms, with Pt(l) carrying PEt 3 and l f -
2-CBioH,, ligands while Pt(2) carries a TeH and PEt 3 group. In the bridge system the Pt(l)-Te(l) and Pt(l)-Te(2)
bond lengths of 272.20(6) and 270.54(6) pm are perceptibly longer than the Pt(2)-Te(l) and Pt(2)-Te(2) values of
261.75(6) and 261.13(7) pm, respectively. This may result from the Pt atoms having different formal oxidation
states with Pt(l) at 4 and Pt(2) at 2.

95
Vol. 29, No. 2, 2006 Structural Aspect of Platinum Coordination Compounds:
Part VI. Heteroborane Platinum Derivatives

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99
Vol, 29, No. 2, 2006 Structural Aspect of Platinum Coordination Compounds:
Part VI. Heteroborane Platinum Derivatives

The structure of a green dimer 1551 is shown in Figure 6. The molecule has two Pt(PEt3)2(&-CB10H]0) units
bridged by an I atom (B(x)-I = 2167(2) pm, B(y)-I = 219.7(6) pm and B(x)-I-B(y) = 112.1(3)7. Moreover, in
both halves of the molecule the boron atoms linked to the I atom are in a ß-site with respect to the C atom in the
{CBBBB} ring ligating the Pt atoms.

Fig. 6. Structure of Pi2(PEt3)4{I(H)(CBioHio)2} [55]

The molecular structure of a colourless dimer /18/ is that of an arachno-diplatina-decaborane which features a
bis(trihapto)B8 unit. The gross structure can be seen as an open faced ten-vertex cluster with a six atom open face.
The structure of an orange dimer /69/ is shown in Figure 7. The structure appears as a three-cluster assembly
based on two nido eleven-vertex {PtB„,} clusters, and a nido eight-vertex {B8} subcluster which is fused to the
central {PtB,„} unit with a common two-boron edge B(2)-B(5).

100
Holloway and Melnik Main Group Metal Chemistry

Fig. 7. Structure of [(PMe2Ph)2Pt(Bi6Hi7)Pt(BioHn.PMe2Ph] [69]

A dark green trimer /70/ is the only example of its type and its structure is shown in Figure 8. The gross heavy
atom cluster structure comprises a 17-vertex polyhedral configuration with a seven-membered {PtB 2 PtBj} open
face [Pt(10), B(9), B(8), Pt(7), B(5% B(4"), B(9")], but with an otherwise deltahedral framework. The structure can
be interpreted in terms of two fused subclusters: (i) an arachno-type nine-vertex 6,,8,-Pt2B7 moiety which has its
Pt(7)-B(7')-Pt(10) atoms in common, and (ii) a nido-type eleven-vertex 2,7,10-Pt3B8 moiety distorted somewhat
from the idealised [B n Hi 4 ]" configuration due to accommodation of the larger Pt atoms. The Pt(2)-Pt(7) distance
of 301.2(1) pm is about 36.4 pm shorter than the Pt(7)-Pt(10) distance of 337.6(1) pm.
In this series there are four types of heteroborane from a bonding point of view, ter-, tetra- penta- and
hexadentate. The mean Pt-B bond distance increases in the order: 221.5 pm (ter-) < 223.5 pm (penta-) < 224 pm
(hexa-) < 227 pm (tetradentate). There are three types of Ρ donor ligands, PMe2Ph, PEt3 and rf-dppe. The mean
Pt-P bond length increases in the order: 228.5 pm (r]2-dppe) < 231 pm (PMe2Ph) < 231.5 pm-(PEt3).

101
Vol. 29, No. 2, 2006 Structural Aspect of Platinum Coordination Compounds:
Part VI. Heteroborane Platinum Derivatives

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4. CONCLUSIONS

This review identifies eighty three monomelic, sixteen dimeric and one trimeric platinum heteroboranes. The
valence state Pt(II) is found in all but one example /40a/, which contains a mixed valence situation of Pt(II) and
Pt(IV) atoms. The Pt atoms are four-, five-, six-, seven- and eight-coordinated, the latter having a sandwich
configuration. The heteroborane moieties are bi- to hepta-dentate. The P-donor ligands are predominantly
PMe2Ph with some examples of PPh3, PEt3 and PMe3 examples. The most common space group is monoclinic
(72 examples) with some triclinic (18) and orthorhombic (10).
From the five well known borane classes only four are found in the chemistry of platinum: closo-
/6,8,10,13,17,19,24,25,29,34,45-49,55,66/, nido- Π,11,20-23,27,28,30,35-42,50-55,59,54,69/, arachno- /9,12,
14,15,18,19,26,44,59,68,70/, and conjuncto- /39,43,56/.
The shortest Pt(II)-Pt(II) bond distance of 262.1(1) pm is found in a dimer /56/. It is 39.1 pm shorter than that
found in the trimer /62/ of 301.2(1) pm.
One example /34/ exists in two isomeric forms, differing mostly by degree of distortion. Another five
derivatives /11,13,25,29,41/ contain two crystallographically independent molecules, also differing mostly by
degree of distortion. All are typical examples of distortion isomerism /33/.
Despite the increasing availability of data retrieval systems, the location of relevant material is not always
simple. One problem is the choice of key words for indexes, resulting in effective invisibility of some material of
structural importance. Some original papers lack appropriate information, as evident from the gaps in the review
Tables. Some material is only available as supplementary material. We hope that this summary will serve a
function by gathering together relevant available material and delineating areas of interest. Related reviews of
organoplatinum and heterometallic clusters are currently in progress.

5. ACKNOWLEDGEMENTS

The authors appreciate the help given by their University libraries, CISTI in Ottawa, Canada, and the British
Library (St Pancras) London, England. The authors wish to thank those who gave permission for reproduction of
original figures, the Chemical Faculty of the Slovak Technical University for their .cooperation in allowing M.M.
to participate, and the Ministry of Education of the Slovak Republic for financial support.

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