Possible Relevance of the Stochastic Structural Reorganizations

Caused by Instability of Fixed Covalent Bonding in Oxy- Bridged Inorganic

and Organic Polymers which is Suggested to be Relevant to a Fuller
Understanding of the Polymeric Structure of Liquid Water
David Grant
Note 13/4/08

The existence of systems of chemical compounds which

continuously undergo a systematic exchange of parts to form a
stable reproducible mixture of related compounds forms a
definable class of matter mainly associated with the liquid phase
or the suppressed liquid cum solid glassy state. This
phenomenon is encountered with poly-oxy acid chemistries
several inorganic elements (e.g. phosphorus, sulphur and boron).
The underlying principles which determine such behaviour is
suggested also to be relevant to the fuller understanding of the
chemistry and physics of liquid water.

Some fifty years ago (the then new methods of NMR and improved
chromatographic separation techniques) showed up serious anomalies in how
pure chemical substances had hitherto been defined.

Some systems of chemical compounds (most typically of pentacovalent

phosphorus oxyacids and their esters) apparently naturally generated under
relatively mild conditions of a complex library of compounds of related
structure which were created by structural reorganizations which apparently
obeyed a set of rules which were found to be generally applicable over a wide
range of chemical situations.
[This phenomenon will also pertain to phosphate diesters in nucleic acids
which seem endowed with the potential to spontaneously undergo structural
rearrangement under physiological temperature (cf. the self splicing of RNA);
part of the original function of the supramolecular structure of DNA when
viewed from the perspective of non-biological or pre-biological chemistry,
could have evolved to stabilize the phosphodiester backbones against the
spontaneous tendency of polynucleic acid to undergo structural
reorganisation. Contact with catalytically active hydroxyapatite crystal lattice
surfaces may, it can be suggested, putatively override this protection and
thereby facilitate RNA and DNA scission and rearrangement a process which
could conceivably be relevant to evolution and pathological genetic mutation
e.g. in cancer (cf. Grant et al, 1992)]

Reorganization of some organometallic compounds and

inorganic polymers
Some such compounds are intrinsically unstable as single
molecular species but exist in stable mixtures where the normal
reorganisation mixtures occur.
Attempts to use conventional chemical logic to prepare single
members of such families of normally stable under randomized
conditions chemical compounds show them to reform the stable
mixture in the absence of catalysts.
The randomisation process can be apparently described by a
rigorous obeyed mathematical model.
Examples of this are
“polyphosphorous acid” and “polytetrachloroethylene”
and normal water which is suggested to exist as an equilibrated
mixture (i.e. (H2O)n polymers are intrinsically unstable as single
molecular species).

Van Wazer in 1962 discussed an illustration of this phenomenon for a

formerly supposed stable molecular structure
“isotetraphosphoryldimethylamide” (I)

Which was originally believed to have been synthesised

according to the conventional “organic chemistry logic” scheme

[(CH3)2N]2P(O)-O-P(O)(OC2H5)2 + 2ClP(O)[N(CH3)2]2 =>

O-P(O)[N(CH3)2]2
 /
[(CH3)2N]2P(O)-O-P(O)
\
O-P(O)[N(CH3)2]2

(I)

Fig. 1

A preparation which was believed to have this structure gave an 31P NMR
spectrum indicating that no (I) molecules remained; an ambient temperature
pyrolysis had evidently remained undetected during an organic chemistry
logic molecular assembly synthesis pathway or during storage.

Many organophosphorus readily undergo a similar liquid state

facilitated “cold-pyrolysis” or “stochastic scrambling” which are
apparently very mild reactions which are not appreciably
exothermic in nature and give near random distribution of
products and those which give highly non-random products
(such reorganizations are associated with more exothermic
processes).
Such ‘scrambled’ mixtures, especially the near-random types
which can be regarded a fairly precisely definable form of
matter seems in general to be the underlying basis of the
stability of glassy state composite materials (such as the reaction
products of Na2O with SiO2).

Other Phosphorus-Based Oxyacid Systems

Polyphosphorous acid –[O-P(O)(-H)-O-]n>2 decomposes rapidly
and non-randomly under ambient temperature conditions to give
phosphine, polyphosphates and some elementary phosphorus.
Attempts to conduct a dehydration polymerization of
phosphorous acid with acetic anhydride however leads to a
quantitative conversion to a highly commercially and
pharmaceutically useful chelating agent, poly-ethane, 1-hydroxy
1,1- diphosphonic acid (e.g. via a rearrangement of an
intermediately formed diacetyl pyrophosphite derivative
(cf Grant 1979).
Polyphosphoric acid is however a structural stable system but
this is really only strictly correct in terms of the existence of
such polymers as part of a random type reorganization
equilibrium of related molecules.
During the equivalent reaction process between acetic anhydride
and phosphoric acid, polyphosphates are formed and these occur
as a randomly reorganised mixture of variously sized chains and
rings (together with scrambling equilibrium determined amounts
of orthophosphoric acid). The random-type-reorganization
process of the (-OH) to the (=PO) linked central structural
building units [P(O)(OH)3 ortho, P(O)(O-)(OH)2 ends,
P(O)(O-)2 middle and P(O)(O-)3 branch groups] in this system,
with values of the ratio (OH)/P(O) between 0 and 3 (bounded by
phosphorus pentoxide and phosphoric acid) gives rise to a range
of molecules which undergo bond interchange and contains P-
O-P linked polymers, cage molecules, ring molecules and chain
molecules occur which exchange parts with each other).
A similar type of behaviour is apparent for phosphate esters,
silicate esters, polysulphides (this basic process of S-S bond
rearrangement also is involved with protein folding and redox
behaviour), polyselenides, arsenates borates and perhaps some
vanadates; a related process seems also to define ligand
exchange on various metal complexes and can be further
exemplified in organic polymer systems (e.g. polyethers).

Evidently the final mixture of such equilibration processes is as

a state of matter determined almost entirely by the process of
structural interchange which enables the achievement of a stable
mixture in which the exchange processes produce composite
material systems in which the exchange process continues to
occur in such a manner as to contribute to the stability of the
mixture. Such stochastic structural reorganisation through
ligand exchange may be viewed as a form of pyrolysis
(e.g. viewed as low temperature “pyrolysis”).
Organo Chlorine Compound Scrambling
Low temperature “pyrolysis” seems to be especially common in
phosphorus, arsenic boron, and sulphur chemistry. This seemed
to indicate an unexpected fundamental difference between such
chemistries and the chemistry of molecules which were
composed entirely of carbon skeletons.
An exception to this rule, however, was found for
organochlorine compounds which (albeit at a somewhat higher
temperature corresponding to organic pyrolysis conditions but
which could be catlaysed e.g. by Fe and Cu salts) (cf. Grant
1974). All chlorocarbons (organic molecules containing the
atoms of carbon and chlorine only) were found to behave
analogously to phosphorus and other inorganic element based
polymer systems and related covalent compounds in that they
tend to undergo spontaneous decomposition to create an
equilibrated mixture of ligand exchanging molecules. This
phenomenon is illustrated by attempts to prepare
polytetrachloroethylene; this type of molecular composition
seems to be intrinsically unstable, it undergoing an apparent
rapid decomposition to give a mixture chiefly
hexachlorobenzene, carbon tetrachloride and hexachloroethane,
tetrachloroethylene and chlorine produced by reversible
exchange process involving both the backbone carbon and
chlorine-carbon covalent structures. The large size of chlorine
atom could be a critical factor which destablises the fully
chlorinated derivative of polyethylene. Such reorganization
processes may involve free radical intermediates as well as an
exchange of electron pair bonds between structures e.g.
visualized in a conventional non-mathematical chemical
structure pictogram by a concerted movement of electron pairs
between structural building units.
It should be noted that the chlorocarbon, organophosphorus,
organosilicon and other prone-to-scramble systems are
accurately definable as a state of matter defined in terms of
mathematical equations similar to those required for
thermodynamically determined equilibration processes (plus in
some cases an additional random sorting of the amounts of the
simplest structural building units calculated by these equations)
which allows the prediction of quantity and nature of the
molecular compositions present in such liquid or glassy forms of
matter (e.g. those giving rise to the inorganic oxy-bridged
polymer systems exemplified by polyphosphates,
polyphosphonates, polysilicates, polysulphates, polysulphides as
well as polyethers).

Organometallic Compound Scrambling

Structural reorganisation of unstable organometallic
intermediates has also been indicated to be a possible modus
operandi of Ziegler Natta olefin polymerisation catalysts (cf
Grant 1974).

Water as a System of Structrually Reorganizing Aggregates

A further pertinent example of structural reorganisation
determined state-of-matter is suggested to be liquid water; cf.,
the hydrogen bond scrambling determined nature of liquid
water is generally regarded as containing aggregates of H2O
linked by hydrogen bonds. This might be written (H2O)n
with values of n being estimated at ca.100 at room temperature.
I.e. normal water is actually ‘polywater’. However like other
unstable polymers it can be suggested that this also forms a
library of randomly sorted structurally reorganized building
blocks..
Polywater then is a real chemical system (on which the
existence of life depends) for which structural reorganization
concept apply. A recent discourse proposes this
in a verbally not mathematically expressed manner (Chaplin
2008).
In this recent attempt to find a chemical model for liquid water a structure model is
visualised where water structure units move to break up existing cluster and help
create a new cluster which is identical to the old one but only contain a proportion of
the original atoms; this creates a fluctuating self-replicating network of water
molecules with localized band overlapping icosahedral symmetry {first proposed to
exist in liquid water in 1998 and detected in water nanodrops in 2001}. The clusters
were considered to form by interconversion between high and low density forms of
water possibly by bending, not breaking, of some of the hydrogen bonds. Structuring
might, it was suggested, also flicker between statistically and topographically
equivalent clusters involving different molecules which shifted their cluster centres.
The anomalous properties of water (including its change in density the temperature
increases its pressure –viscosity behaviour and its the radial X-ray diffraction
distribution pattern) could be explained by the average cluster size, the cluster
integrity and the proportion in the low-density form which all decrease with
increasing temperature (also the model could explain the apparent presence of both
cyclic pentamers and hexamers, the change in properties on supercooling and the
solvation and hydration properties of ions, hydrophobic molecules, carbohydrates and
macromolecules; the concept could also be adapted to a “two state” structural models
of liquid water into which larger molecules can be mapped in order to offer insights
into their interactions) (cf Chaplin 2008).

References

Van Wazer JR (1962)

Structural reorganization through ligand interchange
American Scientist 50: 450-472
Cf., Schwarzman E Van Wazer JR (1961)
J Amer Chem Soc
Principles of phosphorus chemistry. XI. The polyphosphate
esters
J Amer Chem Soc 83: 365-367
Cf also ibid. 1960; 82 6009-6013; cf. p 6013

Grant D Van Wazer JR (1964)

Exchange of parts between molecules at equilibrium. V. Alkyl-
terminated chain polysulfides and polyselenides
Ibid. 86: 3012-3017

Van Wazer JR Grant D Dungan CH (1965)

Exchange of parts between molecules at equilibrium. VIII.
Dimethylpolysulfates
Ibid. 87 3333-3330
Grant D Van Wazer JR Dungan CH (1967)
α ω -disubstuted polymethylphosphonates and
polyphenylpolyphosphonates from condensation polymerization
J Polymer Sci A-1 5 57-75

Grant D (1967)
Redistribution reactions in polymeric alkyl silicates
J Inorg Nucl Chem 29: 69-81

Grant D (1974)
The pertinence of the scrambling behaviour of ligands on
transition-metal centres to Ziegler Natta catalyst activities
J Polymer Sci Polymer Lett Edit 13: 1-9

Grant D (1979)
The rearrangement polymerization of phosphorus acid with
acetic anhydride
Eur Polymer J 15: 1161-1165

Grant D (1974)
The pyrolysis of chlorocarbons
J Appl Chem Biotechnol 24 49-58
Cf Aubrey NE Van Wazer JE (1964)
J Amer Chem Soc 4380-4383

Grant D Long WF Williamson FB (1992)

Degenerative and inflammatory diseases may result from
defects in antimineralization mechanisms afforded by
glycosaminoglycans
Medical Hypotheses 38: 49-55, cf. p. 52

Chaplin M (2008)
Water Clusters: Overview, in
http://www.Isbu.ac.uk/water