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A review (which was originally drafted in 1975) of ideas generated from my participation in J.R. Van Wazer’s ‘Structural- Reorganization-Throughout-The-Periodic-Table’ research program (which had been offered but not published or otherwise put to use) is now re-formatted below.
---------------------------------------------------------------------------------------SCRAMBLING REACTIONS David Grant, B.Sc., Ph.D. During the latter part of the eighteenth century, Berthollet and Proust debated the constancy of the combining proportions of elements in chemical species, (1). Berthollet recognized the importance of equilibria, regarding constant proportions as being the exception. There is a grain of truth in this, e.g., polymeric and amorphous species can exhibit variable compositions, and, while numerous compounds including those based on carbon backbones have a high probability of remaining unchanged for a long time, some substances having central atoms other than carbon at structural centers are intrinsically of lower stability than are purely organic molecular species. This applies to the liquid phase which can facilitate rapid molecular rearrangements to occur (and most especially if this process is fast with respect to the time required to separate the individual molecular species then the scrambled product is what is most commonly encountered). This scrambling, may, however, not be detected by vibrational spectroscopy or by X-ray diffraction. Numerous reaction products, previously though to be single compounds have been found to be the scrambled mixtures which, if at equilibrium will exhibit some reproducible physical properties in a manner similar to that of pure compounds. The most general form of scrambling was established by Van Wazer, (2) (ca. 1955) who extended the earlier concepts of Flory, and demonstrated that equilibria of which the following is typical, are established:
(RO)2>P(O)(OR) (neso) + -O½-P(O)(OR)-O½- (middles) ↔ 2 O½-P(O)<(OR)2 (ends)
(further equilbria are usually measured to distinguish the middles in rings from those in chains, and the ends on long chains from those on short chains. In the phosphate-condensed phosphate systems, branch groups also take part in equilibria like : ends + branches ↔ 2 middles).
The Van Wazer method of characterization of chemical systems is useful for the elucidation of the products of synthetic organometallic chemistry where conventional ‘organic chemical logic’ fails to properly identify the substances formed in any attempted stepwise synthesis of an inorganic molecular structure or a mixed inorganic-organic element (e.g. B, P, As, Si, etc.) - containing derivative. An example of former situation arose is an attempt to synthesize an “isotetraphosphate” structure. While a composition which appeared to contain this structure, as suggested by some physical measurements etc. seemed to have been produced, a later re-evaluation by NMR showed that this structure, if formed initially, had completely rearranged to produce a reproducible mixture, the composition of which could be exactly predicted using the scrambling equilibrium hypothesis suggested by Van Wazer, (3). Such rationalizations were similarly useful for arriving at the correct chemical constitution of a product arising from attempts to prepare octamethyltetraminopyrophosphate (((CH3)2N)2P(O))2O) (OMPA) (cf. 3a) (the reaction product, however showed the NMR spectrum of a completely scrambled mixture of the same stoichiometry. A similarly completely scrambled mixture also apparently arose from attempts to prepared specific polysilicate esters, e.g. RO-(Si(OR)2-(OSi(OR)2)n-O-Si(OR)2-OR (where R is an organic group). Scrambling was first recognized as an important phenomenon in tetra-coordinate Pb chemistry by Callingaert and Beatty in 1939, (4). Ethyl vs. methyl groups were found to scramble , near-randomly, on Pb and some other metal centers. Flory (5), considered that an equilbrium middles + ends ↔ middles´ + ends´ occurred between groups in polyester chains. Forbes and Anderson observed the random sorting of Cl vs. Br on –C< (6) and on other centers. Many cases, for a wide range of ligands and centers, are now known to exhibit scrambling behavior. Classification into near-random or highly non-random systems is often helpful. Many systems are nearrandom, e.g., halogen exchange on -V(O)< (7),
-P(O)< (8 ), Ti (6 co-ord.) (9), -Hg- (2 co-ord.) (10), >Ge< (4 co-ord.) (11), >Sn< (4 co-ord.) (12), >Si< (4 co-ord.) (13), -B< (3 co-ord.) (14), [and also, e.g., RnMX4-n (R = alkyl etc., X = halogen, M = Ge, Sn, Si, etc.)]. Recent interest has been shown in CO exchange in cluster compounds, (15); different sites may exhibit markedly different exchange rates. Cf., Fe3 (CO)12 scrambling (15a). Examples of scrambling in polymer systems are: in polysiloxanes, (16); -silicates, (17); -sulphates, (18); -sulphones, (19); -sulphides, (20); -selenides, (20); -borates, (21); -phosphates, (22); -phosphonates, (23); -ethane, oxy,diphosphonates, (24); -arsenites, (25); -germthioxanes, (26); -(fluoro)arsenious methylimides, (27) and -tin sulphides, (28). Scrambling (at ambient temperature), of alkoxyl vs. Cl groups on -V(O)< is some 107 time faster than on -P(O)< but both systems are similarly random, (19). An example of scrambling on –V(O)< (V(O)Cl3 / (CH3)3Si-O-Si(CH3)3) is shown in Fig. 1
The greater rates of scrambling on transition-metal centers may give rise to ‘fluxional’ activity (rapid, often intramolecular NMR-detected scrambling) (29). The use of transition-metal compounds as catalysts for organic reactions, e.g., in hydrogenation, isomerization and polymerization, seems to be afforded by the scrambling potential at the metal, e.g., scrambling-related polymer generation arises from the α-olefin monomer additions to the metal-centered scrambling centers which are the active sites of the Ziegler-Natta polymerization catalysts. In the polymer chain propagation process the transition-metal forms metal-carbon bonds into which πbonded olefinic bonds insert. This is likely to be a reversible (equilibrium) reaction, but is far displaced towards the polymer form at a polymerization temperature of ca. 70oC (30). Whether isotactic or stereospecific polymers arise during this insertion process seems to be dependent on the rate of structural reorganization of metal bound coligands. A further example of organic reaction catalysis at metal centers is the metathesis of olefins at W and Mo centers, which leads to an apparent scrambling of the alkyl groups about the double bond, (31). Scrambling may be catalyzed both positively or negatively, e.g., phosphorus halides scrambling is accelerated by H2O (32); for boron halides, scrambling is inhibited by bases, (33). There is probably no single type of mechanism which can explain scrambling reactions. Under scrambling conditions a mechanistic approach to the rationalization of chemical reaction products obtained at sub-scrambling temperature, so useful for organic reactions at near-ambient temperatures, is much less helpful for achieving an understanding of scrambling process. The important criteria are now knowledge of the equilibria (perhaps more accurately described as [enthalpy-entropy compensated] extrathermodynamic pseudoequilibria) which govern this behavior, (34). A general (first order approximation) principle of scrambling is that the type of equilibrium (e.g. random or non-random) is dependent on the ligands and is independent of the sites; the rate of scrambling, however, depends on the site, (35). Carbon is the slowest site. Scrambling of hydrocarbons (e.g. at 1000oC) gives CH4, C2H6, C3H8 and char (closed system). Phosphorus hydrides behave similarly (‘char’ now being red phosphorus), as do silicon hydrides, (36).
The outcome of high temperature scrambling behavior of hydrocarbons is derivable from the accurate thermodynamic data which is available for these compounds, and the above scrambled corresponds to a thermodynamic equilibrium. However, at lower temperatures, reversible exchange between aliphatic and aromatic carbon-based systems, occurs. These are likely to be pseudo-equilibria, where the forward and reverse rates are not quite equal, and proceed by different mechanisms; this situation is illustrated by the scrambling of chlorocarbons in sealed-tubes, where all chlorocarbons which have been studied give CCl4, C2Cl6 and C6Cl6, with inappreciable char formation, (37). The phenomenon of aromaticity may be considered to be a double bond scrambling around the ring. Negative catalysis (Fe(CO)3 complexing sites) slow the process sufficiently for individual cyclohexatrienes to be distinguished, (38). In boranes and related compounds, a variety of B···H···B scrambling reactions have been reported , e.g. with B3H8-, (39),
Silicates scramble near-randomly, (17), therefore giving rise to appreciable amounts of a large number of structures. Nucleation of crystallization of a particular structure can remove it form the equilibrium, eventually converting all of the molecules present. [Bond exchange also can lead to flow in compositions beyond the gel point. In inorganic polymers such as silicates bond exchange can lead to flow whereas flow in organic polymers flow most often involves the sliding of the intact molecules over each other]. The formation of quite complicated structures in high yield in pre-biotic conditions could have been an outcome of scrambling reactions and subsequent nucleation of specific sub-types of molecules allowing the formation of specific ‘proteinoid’ and poly-sugar-triphosphate molecules to be achieved in high yield.
References (1) Cf. “ A Short History of Chemistry” , J.R. Partington, Macmilllan, London, 1957, p. 153 (2) “Phosphorus and Its Compounds” Vol I, J.R. Van Wazer, Interscience, New York, 1959; C.F. Callis , J. R Van Wazer, J.N. Schoolery and W.A. Anderson, J Amer. Chem. Soc., (1957),79, 2719; J.R. Van Wazer, C.F. Callis and J.N. Schoolery, (1955), 77, 4945 (3) E. Schwarzman and J.R. Van Wazer, J. Amer. Chem. Soc., (1960), 82, 6009 (3a) cf., e.g., J.R. Van Wazer, Amer. Scientist, ref. (36) (4) G. Caligingaert and H.A. Beatty, J. Amer. Chem. Soc. (1939), 61, 2748 G. Calingaert, H.A. Beatty and H.R. Neal, ibid., (1939), 61, 2755 G. Calingaert and H Soros, ibid., (1939), 61, 2758 G. Calingaert, H.A. Beatty and H. Soroos, ibid. (1940), 62, 1099 (5) P.J. Flory, J. Amer Chem. Soc., (1942), 64, 2205 (6) G.S. Forbes and H.H. Anderson, J. Amer. Chem. Soc., (1944), 66, 931 (7) R.J.H. Clark and P.D. Mitchell, J.Chem. Soc. Dalton, 1972, 2429 (8) L.C.D. Groenwege and J.H. Payne Jr., J. Amer Chem. Soc., (1959), 81, 6357 (9) P.A.W. Dean and D.F. Evans, J. Chem. Soc., A, 1970, 2569 (10) M. D. Rausch and J.R. Van Wazer. Inorg. Chem. (1964), 3,761 Cf. J.C. Lockart, Chem. Rev., (1965), 65, 131 (11) G.M. Burch and J.R.Van Wazer, J. Chem. Soc. A. 1966, 586 cf. Inorg. Chem., 1964, 3, 268 (12) J.J. Burke and P.C. Lauterbur, J. Amer. Chem. Soc. (1961), 83, 326; G.S. Forbes and H.H. Anderson, ibid., (1945), 67, 1911; (1944), 66, 931, G. Calingaert, H. Soroos and V. Hnizda, ibid., (1940), 62, 1107 D. Grant and J.R. Van Wazer, J. Organometal. Chem., (1965), 4,
229 (13) K. Moedritzer and J.R. Van Wazer Inorg. Chem. (1964), 3, 268 and refs. cited; cf J.R. Van Wazer and K. Moedritzer, J. Inorg. Nucl. Chem. (1964), 24, 73 (14) H.K Hofmeister and J.R. Van Wazer, J Inorg. Nucl. Chem., (1964), 26, 1209 M.F. Lappert, M.R. Litzow et al., J. Chem Soc.(A) 1971, 383; (15) L. Milone, S. Aime, E.W. Randall and E Rosenberg J.C.S. Chem. Commun., 1975, 452 T.J. Marks and G.W. Grynkewich, J. Organometallic Chem., (1975), 91, C9-12, F.A. Cotton, D.L. Hunter and P. Lahuerti, Inorg. Chem., (1975), 14, 511. (15a) B.F.G. Johnson, J.C.S. Chem. Commun., 1976, 703 (16) K. Moedritzer and J. R. Van Wazer, J. Amer. Chem. Soc. (1964), 86, 802 (17) D. Grant, J. Inorg. Nucl. Chem., (1967), 29, 69 R.O. Gould, B.M. Lowe and N.A. MacGilp, J.C.S. Chem. Commun., 1974, 720 (18) J.R. Van Wazer, D. Grant and C.H. Dungan, J. Amer. Chem. Soc., (1965), 87, 3333 (19) Unpublished work of D. Grant and J.R. Van Wazer (20) J.R. Van Wazer, D. Grant, J. Amer. Chem. Soc., (1964), 86, 3012 (21) H.K. Hofmeister and J.R. Van Wazer, J Inorg. Nucl. Chem., (1964), 26, 1201 (22) J.R. Van Wazer, C.F. Callis, J.N. Shoolery and R.C. Jones, J. A Amer. Chem. Soc., (1956), 78, 5709 and 5715 C.F. Callis, J.R. Van Wazer, J.N. Shoolery and W.A. Anderson, J. Amer. Chem. Soc. (1957), 79, 2719 D.P. Ames, S. Ohashi, C.F. Callis and J.R. Van Wazer ibid.,
(1959), 81, 6350 M. M. Crutchfield, C.F. Callis, R.R. Irani and G.C. Roth, Inorg. Chem., (1962), 1, 813 L.C.D. Groenweghe, J.H. Payne and J.R. Van Wazer, J. Amer. Chem. Soc., (1960), 82, 5305 E. Schwarzmann and J.R. Van Wazer, ibid., (1961), 83, 365 D.R. Cooper and J.A. Semlyen, Polymer, (1972), 13, 414 J.R. Van Wazer and S. Norval, J. Amer. Chem. Soc., (1966), 88, 4415 L.C.D. Groenweghe and J.H. Payne Jr., J. Amer. Chem. Soc., (1959), 81, 6357 (23) D. Grant, J.R. Van Wazer and C.H. Dungan , J. Polymer Sci., (1967),A-1,5, 57 (24) Unpublished work of D. Grant (Glasgow University manuscript in preparation [(added later: eventually published in Eur. Polym. J. (1979), 15, 1161)] (25) J.R. Van Wazer, K. Moedritzer and D.W. Matula, J. Amer. Chem. Soc., (1964), 86, 807 (26) K. Moedritzer and J.R. Van Wazer, J. Amer. Chem. Soc., (1968), 90, 1520 (27) M.D. Rausch, J.R. Van Wazer and K. Moedritzer, J. Amer. Chem. Soc., (1964), 86, 814 (28) K. Moedritzer and J.R. Van Wazer, Inorg. Chem., (1964), 3, 943 (29) F.A. Cotton, Chem. Brit., (1968), 4, 345 Cf. S. Cradock, E.A.V. Ebsworth, H. Moretto and D.W.H. Rankin, J.C.S. Dalton, 1975, 390; A.J. Campbell, C.A. Fyfe and E. Maslowsky Jr., Chem Commun., 1971, 1032; P.C. Angus and S.R. Stobart, J.C.S. Dalton, 1973, 2374
(30) Cf. D. Grant , J Polymer Sci., Polymer Letters , (1975), 13,1 (31) Cf. N. Calderon and R.N. Hinrichs, Chemtech., (1974), 4, 627 E.L. Muetterties and M.A. Busch, J.C.S. Chem. Commun., 1974, 754 and refs. cited; A.J. Amass, Br. Polymer J. (1972), 4, 327
(32) A.D. Jordan and R.G. Cavell, Inorg. Chem., (1972), 11, 564
B. Benton-Jones, M.E.A. Davidson, J.S. Hartman, J.J. Klassen and J.M. Miller, J.C.S. Dalton, 1972, 2603 Cf. M.J. Bula, J.S. Hartman and C.V. Raman, ibid., 1974, 725 D.W. Matula, L.C.D. Groenweghe and J.R. Van Wazer, J Chem. Phys. (1964), 41, 3105 R.M. Levy and J.R. Van Wazer, ibid., (1966), 45, 1824 L.C.D. Groenweghe, J.R. Van Wazer and A.W. Dickenson, Anal. Chem., (1964), 36, 303 J.R. Van Wazer and K. Moedritzer, Angew. Chem. Internat. Edit., (1966), 5, 341 K. Moedritzer, Inorg. Chim. Acta, 1970, 4, 613 J.R. Van Wazer and L.C.D. Groenweghe, “Nuclear Magnetic Resonance in Chemistry”, B. Pesce, Ed., (1965), 283 J.R. Van Wazer “Inorganic Polymer Chemistry” J. Macromol. Sci., 1967, A1, 29 J.C. Lockart, Chem. Rev., (1965), 65, 131
Note added to ms. later: the Van Wazer scrambling phenomena are likely to be afforded by extrathermodynamic pseudoequilibria associated with enthalpy-entropy compensation phenomena, the general occurrence of which throughout biology, chemistry and physics putatively requires a re-think of classical thermodynamics, e.g. involving reverse time and vacuum energy concepts ]
J.R. Van Wazer, Proc. Conf. Coord. Chem., 8th, Vienna, 1964, Springer-Verlag, Vienna, Ed. V. Gutman, p.162
(36) J.R. Van Wazer, Amer. Scientist, (1962) , 50, 450 (37) N.E. Aubrey and J.R. Van Wazer, J. Amer Chem Soc., (1964), 86, 4380 D. Grant, J. Appl. Chem. Biotechnol., (1974), 24, 49 (38) R. Victor, R. Ben-Shoshan and S. Sarel, Chem. Commun., 1970, 1680 (39) H. Beall and C.H. Bushweller, Chem. Rev., (1973), 73, 465 cf, E.L. Muetterties, E.L. Hoel, C.G. Salentine and M.F. Hawthorne, Inorg. Chem., (1975), 14, 950 Further References, Scrambling Centre Indicated. J.R. Van Wazer et al, J. Inorg. Nucl. Chem. (1964), 26, 1209 (boron);
Inorg. Chem., (1964), 3, 139 (arsenic); J. Amer. Chem. Soc., (1964), 86, 811; Inorg. Chem., (1964), 3, 280 (phosphorus); Ibid., (1965), 4, 1294 (silicon) (silicon, germanium) J. Inorg. Nucl. Chem., (1964), 26, 737 (silicon) J. Organometal. Chem., (1968), 12, 69 (silicon) Ibid., (1975), 85, 41 ([silicon] phosphorus) Inorg. Chim. Acta. (1967), 1, 407; Ibid., (1967), 1, (1967), 152 (silicon, germanium) (cf. K. Moedritzer ibid. (1971), 5, 547; (1974), 10, 163 (silicon, germanium K.M. Abraham and J.R. Van Wazer, J. Inorg. Nucl. Chem., (1975), 37, 541 (silicon, germanium) E. Fluck, J.R. Van Wazer and L.C.D. Groenweghe, J. Amer. Chem. Soc., (1959), 81, 6363 (phosphorus) J. Inorg. Nucl. Chem., (1967), 29,1571 (germanium); Ibid. (1964), 26, 737; Ibid., (1967), 29, 1851 (silicon) Inorg. Chem., (1965), 4, 1294 (review) J. Chem. Phys. (1964), 41, 3122 (several elements) J.G. Reiss and S.C. Pace, Inorg. Chim. Acta, (1974), 9, 61 (silicon) M.W. Grant and R.H. Prince, J. Chem. Soc., (A), 1969, 1138 (silicon)(germanium) F. Glocking, S.R. Stobart and J.J. Sweeney, J.C.S. Dalton, 1973, 2029 (mercury); A.G. Lee and G.M. Sheldrick, ibid., (A), 1969, 1055 (thallium); J.A.S. Howell and K.C. Moss, ibid., (A), 1971, 2483 (tantalum); R. Davis, M.N.S. Hill, C.E. Holloway, B.F.G. Johnson and K.H. AlObaidi, ibid., (A), 1971, 994 (molybdenum and tungsten); H. Hagnauer, G.C. Stocco and R.S. Tobias, J. Organometal. Chem., (1972), 46, 179 (gold); C.E. Holloway, J. Coord. Chem., 1971,1, 253 (tantalum); J. Evans, B.F.G. Johnson, J. Lewis and J.R. Norton, J.C.S. Chem, Commun., 1973, 807 (rhodium); J.F. Nixon, B. Wilkins and D.A. Clement, J.C.S. Dalton, 1974, 1993 (rhodium); J. Evans, B.F.G. Johnson, J. Lewis and R.Watt, ibid., 1974, 2368 (rhodium); M. Green and G.J. Parker, ibid., 1974, 333 (rhodium and iridium); A.J.P. Domingos, B.F.G. Johnson and J. Lewis, ibid., 1974, 145 (ruthenium); T.H. Whitesides and R.A. Budnik, J.C.S. Chem. Commun., 1974, 302 (ruthenium);
F. Calderazzo, M. Pasquali and T. Salvatori, J.C.S. Dalton, 1974, 1102 (uranium); R.J. Cross and N.H. Tennent, ibid., 1974, 1444 (platinium); T. Mole, Organometal. Reactions, (1970),1,1, (review, aluminum); N.S. Ham and T. Mole, Progr. Nuclear Magnetic Resonance Spectrosocpy, Ed. J.W. Feeney and L.H. Sutcliff, Pergamon Press, London, (1969), 4, 91 (review); F.A. Cotton, Accounts Chem. Res., (1968), 1, 251 (review). (Examples of scrambling on carbon); K. Moedritzer and J.R. Van Wazer, J. Org. Chem., (1965), 30, 3920 (polyoxymethylenes); Ibid., (1965), 30, 3925 (acetals and orthoformates) J.T. Bursey , M.M. Bursey and D.G.I. Kingston, Chem. Rev., (1973), 73, 191 (intramolecular hydrogen transfer on carbon during mass spectrometery).
Added Later Following my postgraduate research (which had been funded by an Albright & Wilson Mfg. U.K. Studentship and supervised by D.S. Payne at the University of Glasgow, Scotland, U.K, (earning Ph.D. in 1962 for a thesis ‘A Study of Phosphites’ [cf. D. Grant et al., J. Inorg. Nucl. Chem., 1964, 26, 1985 and ibid., 26, 2103) and a study of the use of Ce(IV) for oxidative analytical chemistry [Anal. Chim. Acta, 1961, 25, 422 ]), I had the honor to work as a Postdoctoral Fellow with John R Van Wazer in his (Monsanto Co, St Louis) research group (which conducted fundamental researches into the phenomenon of stochastic structural reorganization; this processes, which had been found to determine the chemical constitution of condensed phosphates (and further seemed to offer insight into the in biological use of condensed phosphates for energy transfer and as a basic determinant of the structure and activity of nucleic acids), also seemed to allow for a fuller understanding of the thermal stability of numerous kinds of substances (including inorganic, organometallic and organic polymers). I later contributed to I.S.R. U.K. research activities (which ceased in 1975) [cf., e.g. E.W. Duck et al. Eur. Polymer J., 1974, 10, 77; ibid., 481; ibid., 1979, 15, 625) and, “The Pertinence Of The Scrambling Behaviour of Ligands on Transition-Metal Centres to Ziegler-Natta Catalyst Activities” (J. Polymer Sci., Polymer Lett., 1975, 13, 1 ) which suggested that the polymerization of olefins (as well as the related process of olefin metathesis) occurred by a process akin to Van Wazer structural reorganization at the catalytic center monomer adducts].