MOLECULES FOR CARRORANY.. (UI PENNSYL VANIA SATE UNIVUNIVERSITY PARK DEPT OF CHEMI STRY H R ALLCOCK

UN:IASSFEU 05 DEC 83 TR 30 N0O 14-75-C 0685 F/G 7/3 NL

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MICROCOPY RESOLUTION TEST CHARTNATIONAL KIRAl F)I AlANF A01 FF(>, A

%ECU.IITY CLASSIFICATION OF THIS PAGE (When Dole Entered)A

REPORT DOCUMENTATION PAGE BEOECMLE143FRI. REORT NMBER 2. GOVT ACCESSION NO. I. RECIPIENT'S CATA6OG NUMBER

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CYCLIC AND HIGH POLYMERIC PHOSPHAZENES AS CARRIER Interim Technical ReportMOLECULES FOR CARBORANYL, METALLO, OR BIOACTIVE ______________

SIDE GROUPS S. PERFORMING ORG. REPORT NUMBER

7. AUTHiOR(@) S. CONTRAC 0GRAN MIUMmER()

H. R. Alicock N00014-75-C-0685

9. PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM ELEMENT. PROJECT, TASKAREA A WORK UNIT NUMBERS

Department of Chemistry N 5-7The Pennsylvania State University N 5-7University Park, Pennsylvania 16802

%4II. CONTROLLING OFFICE NAME AND ADDRESS 12. REPORT DATE

Department of the Navy December 5, 1983Office of Naval Research 13. NUMBER OFPAGES

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Is. SUPPLEMENTARY NOTES

To be published in ACS Symposium Series '

C6. Polymers. Phosphazenes, organometallic, biomedical, carboranes

C-D

L" 20. ABST RACT (Continue an reverse aide If necessary and Identify by block numb*?)

2Cyclic and high polymeric phosphazenes can be modified by nucleophilic-typesubstitution reactions to generate a wide range of derivatives. Recentdevelopments include the introduction of bioactive organic residues to yieldbiologically-active high polymers and the synthesis of transition metalderivatives of phosphazenes. In addition, hybrid phosphazene-carboranecompounds have been prepared including examples in which nido-carboranylunits, attached to a phosphazene ring o; chain, function as binding sites fotransitio meta 9_An~-h~ r~q

DD , jRR7 1473 EDITION OF I NOV 65 IS OBSOLETE

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OFFICE OF NAVAL RESEARCH

Contract N00014-75-C-0685

Task No. NR 356-577

TECHNICAL REPORT NO. 30

Cyclic and High Polymeric Phosphazenes as Carrier Moleculesfor Carboranyl, Metallo, or Bioactive Side Groups

by

Harry R. Allcock

Prepared for Publication

in the

ACS Symposium Series

The Pennsylvania State University

Department of ChemistryUniversity Park, Pennsylvania

December 5, 1983

Reproduction in whole or in part is permitted for

any purpose of the United States Government

This document has been approved for public releaseand sale; its distribution is unlimited

" I ,. 4 , - . . ,=,' 'r :,

ACS Symposium Series -"Rings, Cases, and Polymers of the RepresentativeElements"

CYCLIC AVID H GH POLDIERC PHOSPHAZENES AS CARI!R .'IOLECULFS FORCAIDORAYL. .MTALLO, OR BIOACTIV. SIDE GROUPS

H. R. ALLCOCK

Departzent of Chemistry, The Pennsylvania State University,University Park, Pennsylvania 16802

Cyclic and high polymeric phoephazenes can bemodified by nucleophilic-cype substitution reactionsto generate a wide range of derivatives. Recentdevelopments include the introduction of bioactiveorganic residues to yield biologically-active highpolymers and the synthesis of transition metalderivatives of phosphazones. In addition, hybridphosphazene-carborane compounds have been preparedincluding examples in which nido-carboranyl units,attached to a 9osphaza" ring or chain, functionas binding sites for transition metal organometallicunits.

.4st inorganic research involves work with small molecules.end relatively little concentrated effort has been devoted to themacroolecular aspects of the subject. The complexity of themacromolecular chemistry has undoubtedly contributed to thisneglect. Rowever,.it is clear from recent work that dramaticadvances in both fundamntal science and technology would bepossible if the high polymer chemistry of the representativeelements were to be studied in detail. Indeed, the much-heralded renaissance in Main Group chemistry may ultimately dependon a closer investigation of the macromolecular aspects of rhefield.

Mfy purpose here is to illustrate what can be accomplishedwith just one inorganic mecrouolecular system - in this caseconstructed from a backbone of phosphorus and nitrogen stow . AAlmost certainly, other system based on the .ain Group elementscan be developed to an equal or greater degree. I hope that thefollowing comments will stimulate an increased interest in thatdirecton. I will also attempt to illustrate the relationshipbetween the fundamental chemistry on the one hand. and an approach ession Forto solving practical problem on the other. S AI

i-C TABUnannouncedJustIficatior

Distr ibution/

Availability Codes

Dit Avail and/orDist I Spec lal

Guiding Principles

Yearly all synthetic polymers are synthasized by the polymer-ization or copolymerization of different "mnomers." The chaingrowth process say involve the addition chain reactions ofunsaturated small molecules, condensation reactions, or ring-opening chain-coupling processes. In conventional polymerchemistry, the synthesis of a new polymer requires the use of anew monomer. This approach is often unsatisfactory for inorganicsystems, where relatively few monomers or cyclic oligomers can beinduced to polymerize, at least under conditions that have beenstudied to date. The main exception to this rule is thecondensation-type growth that occurs with inorganic di-hydroxyacids.

Because the opportunities for controlled chain growth aremre restricted in inorganic than in organic systems, an alter-native approach to polymer synthesis becomes appealing. This

involves the use of substitution processes carried out on apreformed reactive polymeric intermediate. In this way moleculardiversity can be introduced by different substitution reactionsrather than by s diversification of the polymerization process.

If this principle can be applied, two pocential problems mustbe avoided: the substitution reactions must lead to neither chaincleavage nor crosslinking.

Simple Substitution Reactions with Polv(dihalophosphazenes)

Poly(dichlorophosphazene) (II) is a highly reactive inorganic

macromolecule. It can be prepared by the carefully controlledthermal polymrization of the cyclic crimer, hexachlorocyclocri-phosphazene (I), itself synthesized from phosphorus pentachlorideand amnium chloride. In solution, the chlorine atoms in I1 canbe replaced readily by reaction with a wide variety of organicnucleophiles (1,2,3) (Scheme 1). The resultant polymers (111-v)are stable and display a range of physical and chemical propertiesdetermined by the nature of the organic side groups. Thissynthesis process has been reviewed in detail elsewhere (4-7).Here it is sufficient to note that several hundred poly(organo-phosphazenes) have been prepared by this method. Polymers of

this type are already being used in technology; they are also ofconsiderable scientific interest. Similar syntheses have beendeveloped based oan poly(difluorophosphazens), (PF 2)5 (8).

..0 -

. _ 5

ii(n a 15,000)P" , c P-' C (MW a2 z 106 )

\ A7K0ma fri 2

oP~ _N P n.

Scheme 1

Cyclic Trimers and Tecramrs as Reaction Models

From a theoretical and mechanistic point of viev, smallmolecule rings are msch easier to study than long macronolecularchains. Substitution reactions carried out on macromolecularsubstrates may involve side reactions that load to chain cleavageor crosslinking. Mechanistic studies vith mcromolecules aredifficult to carry out because of solution viscosity effects,distributions in chain length, and the problem of character-ization. Rence, it is prudent to eplore potential new reactionsfirst with the use of small molecule models such as I, V., and V11and then to eteud these reactions to the high polymers.

J_ _&

C1 C3. T Flp I I

P P Cl - P N-P -Cl-N '\ 1 -

Cil N 1 71 NSJ It,/%I I II I

p C ,P PN l-P N P-C

Ci. Cl

I VI 7II

Some of the polymeric reactions mentioned below are still under

study at the model compound level.

Modern Objectives Ln Polymer Synthesis

Polymers have been valued since antiquity for their solidstate properties. By this is meant cheir ability to undergochain entanglement or co-linear orientation aid microcrystalli-zation in the solid state. This underlies their use asstructural mterials, films, fibers, and alastomers. Suchproperties still constitute the driving force for most polymer-oriented research, especially with respect to :he synthesis ofheat-stable, radiation-stable, or highly flexible materials.The electrical properties of solid polymers have always been ofinterest.

However. in recent years another approach to polymerchemistry has received increased emphasis. In this, macro-molecules are studied in terms of their behavior as sinalemolecules rather than as molecular conglomerates. In solution,polymer molecules behave differently from smell moleculesbecause the long chain length permits extensive coiling, reducedtranslational mobility, and an inability to pass through semi-permeable membranes. Lightly crosslinked polymers behave likelinear polymers in solution except that the swollen matrix has aphysical immobility and an open matrix character unlike any othersystem. For these reasons, polymers are of great interest as"carrier molecules" for chemotherapeutic drugs or transitionmetal catalysts.

Finally, single macromolecules, because of their one-dimensional character, offer the promise of sequential side groupcoding, information storage, and template function in the mannerthat is well known in biological polymers (Figure 1).

Conventional synthetic organic polymers are being studiedfor all of these reasons, but the general lack of chemicalreactivity in these systems is a serious drawback. It is forthis reason that polyphosphaene, with their substitutive

II0

6U)

hi024 a

04 IMA

3ww

method of synthesis, are of considerable interest. In thefollowing sections, I will illustrate vhy the polyphosphazenesystem is an appealing starting point for now developments in twospecific areas - in chemotherapy and polymer-bound catalyst york.

Bioactive Polyphosphazenes

Specific inorganic macromolecules are unusual because theycan be hydrolyzed to relatively innocuous products or to smallmolecules that can be metabolized. Most conventional organicpolymers do not have this attribute. Thus. these inorganicsystems are of special interest as carrier molecules in chemo-therapy.

Recent work in our laboratory has shown that certain sidegroups attached to a polyphosphazene chain impart a sensitivityto hydrolytic chain cleavage; ocher side groups generate water-solubility. Both of these characteristics are important inchemotherapy. Polyphosphazenes are also valuable in biologybecause two or more substituted groups can be readily attachedto the same chain. Thus. individual side groups that possesschemotherapeutic, vater-solubilization, hydrolytic-destabilization,or 'homing" characteristics can be combined in one molecule toform a drug vith a set of synergistic properties.

Polymers containing the repeating units shown in VIII-XIhave been shown to be hydrolytically degradable and/or water-soluble (9-13). Amino acid ester derivatives (VIII) degrade toethanol, amino acid, phosphate, and amonia, vhich can either bemetabolized or excreted. Thus, such side units used togethervith chemotherapeutic cosubstituent groups, provide a facile drugdelivery system. Imidazolyl side groups (IX) also conferhydrolytic sensitivity, but the biochemical response to thehydrolysis products has not vet been established. aethylaminoside groups X) provide vater-solubility, as do glucose residues(XI).

- I,- 2 p 2COOqt .

P P

TII

0 !

0

I

"0 2 01,

These polymers ere synthesized by the general methods shown inScheme 1. Their hydrolysis behavior has been the subject ofsveral fundamental mechanistic studies at the model compoundIvel (10,11).

The attachment of biologically-active side groups has alsobeen explored. At the present time several different approacheshave been developed vhich lead to the synthesis of polymers suchas XII-XMI.

, II

.T C(O33 OR

I ]IIN

Cl2COO:'t Oph

(2) 2" Et 1< 2 111 %OPItI S P"

Et

XIV 17

OR 03

-,I -P- CH 2CH 2M2HIOPh

Ol . 2 XfEt 3 Reparin

N .?

Steroid-bound polyphosphazenes (XII) can be prepared by thereaction of II vith metal steroidoxide salts folloved by treatmentwith amino acid esters (14.15). The sulfadiazine-bound polymer(.aII) was synthesized by Schiff's base coupling of a polvphos-phazene bearing a pendent aldshydic group with the antiobiocicasine (16). The local anesthetic, procaine, was linked to thepolymer backbone by direct aminolysis of TI to yield polymersbased on the repeating unit XIV (17). Peptide-couplingtechniques have been used for the linkage of polyphosphazenesbearing pendent amino residues to bioactive carboxylic acids (XV)(I.). Catecholamines, such as dopamine or epinephrine, have beenLinked to ar.loxyphosphazene high polymers by diazo couplingmethods (XV) (19), and these polymers retain the biologicalactivity of the free hormone. The mcopolysaccharide, heparin,can be bound to aryloxyphosphasene polymers via ionic exchange

with quaternized ammonium pendent groups CXVII) (20). Thesepolymers show promise as non-thrombogenic materials for bio-engineering.

It will be clear that, combined with the use of hydro-lyticaly-sensitizing or water-solubilizing cosubstituent groups,these polymsrs could have an important impact on chemother -v andother areas of biomedicine. At present, the problem isestablish the feasibility of a wide range of synthetic me- isand to evaluate the biological activity of each class of aers.

Linkage of Transition Metals to Phosphazene Pings and HiPolvymrs

This book comprises a survey of recent advances inchemistry of the representative (Main Group) elements.the long-range resurgence of Main Group chemistry as an exi-ndingresearch area depends to some extent on the strength of its inter-face with organic chemistry, transition metal chemistry, andapplied science. Some organic-related aspects of phosphazenechemistry were discussed in the previous section. Here theinterface with transition metal chemistry is reviewed.

Polyphosphazenes and cyclophosphazenes are almost unique ascarrier molecules for transition metals because of the wide rangeof binding sites that can be incorporated into the phosphazenestructure. The substitutive mode of synthesis described earlierallows a structural diversity that is not found, for example, inpolystyrene, polyphenylene oxide, or other organic carrierpolymers.

he emphasis in the following sections will be on exploratorymodel reactions carried out with phosphazene cyclic trimers ortetramers, although the analogous macromolecules systems have alsobeen studied in several cases. First, I will summarize thevarious types of metal binding sites that are accessible at thepresent time. Synthetic procedures leading to the incorporationof several of those sites and their role in metal binding willthen be discussed.

Options for Metal-Binding Sites. Seven approaches formetal-binding to cyclic or polymeric phosphazenes have beenexplored in our laboratory. These are sumarized in structuresXVI!I (21). M (22-25), . (26). I (27), II (28,9), III(30). and MXV (31.32.33).

t' o

MCI 1ni I

Only three of thtse approaches will be discussed here. Theothers can be traced through the references given.

?andent Fhosphine Groups. The classical method !or thelinkage of transition metal units to high polymrs is via pendentphosphine groups attached to a mcromolecular chain. We havedeveloped a synthetic strategy for the preparation of cvclophos-phazene model compounds and the corresponding linear high polymersthich bear pendent triarylphoaphine groups. This approach isillustrated in Scheme 2 (22-25).

4 i

XaOC I5x P A, S - hO61F .) - 3- P-

I -iACI ICl. 0Th

0 i hh

I -LI I.. -

01Th 0T:h

Schag. 2

Typical products prepared by this route include XXV, XYV, and

Pho 0 P 0 0 700

11 0 h, Ph2 j-

,h 'O~h Ph 2P -a ~o' O\ 1 110P 1.

II

xxv

PPh21

(N 'I :n~ 7.000)

L0 0

Q6~

I- 1

Species such as XXV, .XVI. or XXVII readily form coordinationcomplexes when treated with AuCI, R'Os (CO) 1 0 . .(CO) 3 (n-C 5 H5 ),Fe(CO) 3 (PhC-CNC(O)CR3). or (hCi(CO)I? 2 (U). Two results areof special interest. First, the skeletal nitrogen atoms in XVV-XX"II do not participate in the coordination process. Presumably,they are effectively shielded by the aryloxy units and are of lowbasicity. Second. :-dinative crosslinking can occur when twophosphine residues '.nd :o one metal atom. LiSand-exchangereactions were detected for the rhodium-bound species. Thetri-osmiua cluster adducts of .WV, XXVI, and XMVII are catalystsfor the isoeerization of 1-hexane to 2-hexane.

Carboranyl Phosphazenes. Cyclic trimeric and highpolymeric chlorophosphazenes react with lithlocarboranes to formcarboranyl phosphazenes, as shown in XXVII and WXXX (28).

P

X Ii

(0 - IN)

R - .- or Ph, and X Cl or OCHCF 3 (4 C)

The halogen atoms remsininS can then be replaced by organicresidues such as trifluoroethoxy umits. High polymers can alsobe prepared by ring-opening polymerization of the chlorocyclo-phosphazene, XXVII. Compounds of this type can be converted toaido-carboranes in the presence of base, but theme do not formmetallo-derivatives, presumably for steric reasons (29).-

However, separation of the carborane cage from M1 e phos-phazene ring or chain by a methylene spacer group allows atalsto be inserted into the open face of the carborane. Thesesyntheses were accomplished by thd reaction routes shown inSchemes 3 and 4. igh polymeric analogues of these trans-formations have also been accomplished following polymerizationof Ma. The rhodium-bound cyclophosphazenes and polyphosphazenesare catalysts for the hydrogenation of 1-hexene. In this, theyshow a similar behavior to metallocarboranes linked to polystyrene

Cl Cl Ime H .4a CHt -C

\ eN N 2N N (B NC" N MeN 4-

N'1 1" l agi c II ucl DrCH 2 CO CE l 1 11" Clp p 1 - P P- IN P P

cl lo "Cl Cil -I 'ci -78*C C1 4-N Nci

B 3 1 A ( C

I3C N ) 2

me CH

. 2 CH 2 / 2-

10 o~ CI R N N NC5j

,,I II/, p p1\ 1 11

c'N "Cl 5 10 N 5 510

H

o - Eli

-C

Scham 3

.40 CH 2--

p

c o N#" Nc o

S'lw" 5 10*.IIcso

E\H 2

CHN

2 - - N CH 2- e2,a

LON/510 \ I / 51110

C HX"NCT H N N'o P k N- NC H

(Ph 3P)., HPh, (CO) 3H

.50 C 2 A\ 2 iI, - 2

p P 3

N@, N P ,(CO),,

C5R0 N N NC 5 10 C 5 10N/ % ' N 5NC H0

5cheme 4

L ... .. ... .. . .. . . .. . . .. . . .. ...... .. .. - ...... ,j- ...- -, *.. ,. , -.-_ . r" - 4: . ',. , :. . ."

(34). The oxidative-stability of the phosphazene backbone isexpected to be an advantage in catalytic reactions.

• etallohophazenes with Phosphorus-.Metal Bonds. Untilrecently, the chemistry of cyclic and high polymeric phosphazeneswas essentially the chemistry of their organic derivatives (Scheme1). However, a discovery reported in 1979 (31) opened up a newfield of metallophoephazene chemistry in which transition metalsform the nucleus of the side group structure and are linked tothe skeleton through phosphorus-metal bonds. These species areof theoretical and potentially practical importance, and I Villsummarize briefly some of the main features known at this time.

Organometallic anions react with halophosphazenes to replacehalogen atoms by organometallic units. The first reactions ofthis type discovered are illustrated in Scheme 5. The metallo-phosphazenes are surprisingly stable. Moreover, as shown below,hexachlorocyclotriphosphazene reacts with an organometallic di-anicn to yield both a dimetallo derivative (=CI) and a tri-metallic cluster derivative (MXMII). The latter compound is

Ci N cl

I re 2(C)SI I 2I

(OC)Fe.Fe(O)4 Fe(OoF .\\ 3( c0 0 4r, YO ( co ) ?a / -(\ co ) 3

S"° P R Fe(CO)3Xi IN ici

Z Z 1 1 - CCl P\ P% C C C I

UU

C-4h

S: 9L

z 96 mb Z-9 Z=9

Lb U

Lfb __

8b L

96

22

/,\ \ N 6L

stabilized by both P-metal and N-metal coordinative bonds. Otherme|allophosphazones containing Pt and Au have been reportedrecently by Schaidpeter and coworkers (35). X-ray structuredata have been obtained for several of these compounds and, asmight be expected, a strong interaction between the metallicunits and the phoephazene ring system is evident (31,32,.33,36).

Conclusions

The reactions discussed in this chapter are illustrative ofthe chemical diversity that follows from the substitutiveapproach to polymer synthesis. Rings and polymers based on theMain Group inorganic elements are especially appropriate for thisapproach because of the generally high reactivity of, forexample, the element-halogen bonds. Thus, a key problem facingthe inorganic research community is to devise and developmethods for the synthesis of high polymers, comparable to poly-(halophosphazenes), that contain elements such as silicon,aluminum, boron, or sulfur in the skeleton, with reactive sidegroups attached to these atoms. Once these polymers have beensynthesised, a diverse arsenal of side group substitutionprocesses can then be mobilized to prepare a broad range ofdifferent mcromolecules. If this can be accomplished, itshould have an almost unprecedented impact on inorganicchemistry, polymer chemistry, and high technology.

Acknowledsments

The work described in this chapter was funded by the U.S.Army Research Office, the Office of Naval Research, the NationalInstitutes of Health, VASA, and the National Science FoundationPolymers Program. It is a pleasure to acknowledge thecontributions of my recent coworkers, especially T. J. Full.er,K. Matsumura, T. L. Evans, P. Z. Austin, T. X. .eenan, K. D.Lavin, N. M. Tollefson, G. H. Riding, R. A. Nissan. P. R. Suszko,M. S. Connolly, J. L. Desorcie, P. J. Harris, A. G. Scopelianos,M. L. Lavin, and R. J. Ritchie. Those coworkers who contributedto the earlier work are cited in the list of references.

Literature Cited

1. Allcock, H. I.; Kugel, R. L. J. Am. Chas. Soc. 1965, 87,4216.

Z. Allcock, H. R.; Kugel, R. L.; ValAn, K. J. Inors. Chen.1966. 5. 1709.

3. Allecak, H. Rt.; Kugel, Rt. L. Inosi. Chem. 1966, 5, 1716.

4. ALlcock, "Phosphorus-Nitrogen Compounds"; Academic Press:.New York, 1972; Chapters 15 and 16.

5. Allcock, 1. R. 1.vtroseX. Cha. (Proc. ZUPAC Conf. on Macro-molecules, Florence, Italy, 1980), 1981, Suppl. t_, 3.

6. Sin8ler, i. E.; HapVauer, 0. L.; Sicka, R. W. ACS. Syn. Ser.

1982. p.11.7. Tat*, D. P. J. Polms. Sel. Polym. Syu. 1974. 48, 33.8. Evans, T. L.; Allcock, H. 1. J..4acromi. Sct. - Chem. 1981,

A16, 409.9. Allcack, H. R.; Fuller, T. J.; Mack, 0. P.; (atsummua, K.;

Swnltz, K. M. .acroolecules. 1977, 10, 824.10. Allcack, R. R.; Fuller, T. J.; %Macsmra, K. Inors. Chou.

1982, 21, 515.11. AlIcock, U. L; Fuller, T. J. J. Am. Chem. Soc. 1961, 103,

2250.12. Allcock, R. L; Cook, W. J.; Mack, 0. P. Tunot. Chem. 1972,

11, 2584.13. Alcock, R. R.; Scopelianos, A. G. .acromleculee. 1983,

In press.14. Allcock, 3. 1.; Fuller, T. J.; Matsmura, K. J. Ors. Chen.

1901, 46, 13.15. Alicock, R. R "iller, T. J. Macromolecules. 1980, 13, 1338.16. AlIcock, R. R.; Austin, P. 1. MacroU1ecUe.. 1981, 1, 1616.17. Allcock, H. I.; Austin, P. E. acroulecules. 1982, 15, 680.18. Allcock, R. L; eenan. T. .; goesa, W. C. .acramoecules.

1982, 15, 693.19. Allcock, H. i.; ymr, W. C.; Austin, P. 1. Mfacromnlecu es.

1983 (in press).20. N enan, T. X.; Alcock, R. I. Blouaterials. 1982, 3, 78.21. Allcock, R. I.; Allen, R. W. ; O'Irrion, J. P. 3. Am. Ch m. Soc.

1977, 99, 3984.22. Evans, T. L.; Fuller, T. J.; Allcock. H. R. J. As. Che. Soc.

1979, 101, 242.23. Allcock, I. I.; Evans, T. L.; Fuller. T. J. nors. Chea. 1980,

19, 1026.24. Allcock. R. L; Fuller, T. 3.; Ivans, T. L. Macroeolecules.

1980. 13, 1325.25. Allcock, R. R.; Lavin, K. D.; Tallefson, N. M. Orsanoemcallics.

1983, 2, 267.26. Harris, P. J.; Nissan, 1. A.; Allcock, H. R. J. As. Chem. Soc.

1981, 103, 2256.27. Suasko, P. I.; Whittle, R. R.; Allcock, R. R. J. Chen. Soc.

Chen. Comn. 1982, 960.28. Allcock, H. I.; Scopelisoe, A. G. O'Brien, J. P.; Seruheii,

.4. Y. J. Ast. Chem. Sac. 1981. 101. :350.

29. Allcoci, IT.Scopo1iLnos, A. G.; Tollefsan, X. K.; Whittle,Rt. 1t. J. As. Chem. Sac. 1983, M.5 1316.

30. Allck, R. R.; Greig8er, P. P.; Gardner, J. E.; Schmutz,J. L. J. 1979, I 606.

31. Grelga-F1Tr, 7W cock, H RT. J. Am. Chem. Soc. 1979, 101,

2492.32. Alicock, H. I.; Greliger, P. ?.; Waner, L. J.; leruhein,

M. Y. Inors. Chem. 1981, 20, 716.

33. Allcock, H. I.; Wasner, L. J.; Lavin, X. L. 3. Am. Chem. Soc.1983, 105, 1316.

34. Paxson, T. E.; avthorne, 14. F. J. Am. Chem. Soc. 1974, 96,4674.

35. Schmidpeter. A.; Blank, K.; Riffel, H. Angev. Chem. 1980, 92.36. Suszko, P. R.; Whittle. 1. R.; Alicock, R. R. J. Chem. Soc.

Chem. Comun. 1982, 960.

.... - A', *.

Figure 1. Traditional and exploratory uses for high polymers. (a) Polymers

have been used traditionally for their solid state, chain entanglemenc

behavior vhich gives rise to strength or elasticity. (b) Polymers used as

carrier molecules for bioactive agents are under investigation in controlled-

release drug therapy either as targeted macroolecular drugs or as immobilized,

biodegradable system. (c) Transition metal catalysts linked to polymers

can be immobilized for ease of manipulation or recovery, or the polymer may

modify the catalytic activity. (d) Electrical conduction in polymers may

occur along =saturiced chain sequences or betveen chains in crystalline

domains. (e) Sequential arrangement of side groups along a linear polymer

chain offers the prospect of control of polymer conformation, or the use of

such polymers as templates for the controlled construction of complementary

polymer molecules. Such polymers amy also prove useful in the future for

infor mtion storage at the molecular level.

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Or. C. L. Schilling Dr. R. SoulenUnion Carbide Corporation Contract Research DepartmentChemical and Plastics Pennwalt CorporationTarrytown Technical Center 900 First AvenueTarrytown, New York King of Prussia, Pennsylvania 19406

Dr. A. G. MacDiarmid Dr. G. GoodmanDepartment of Chemistry Globe-Union IncorporatedUniversity of Pennsylvania 5757 North Green Bay AvenuePhiladelphia, Pensylvania 19174 Milwaukee, Wisconsin 53201

Dr. E. Fischer, Code 2853 Dr. Martin H. KaufmanNaval Ship Research and Code 38506

Development Center Naval Weapons CenterAnnapolis, Maryland 402 China Lake, California 93555

Dr. H. Allc Dr. C. AllenDepartm of Chemistry Department of ChemistryPenn v ania State University University of VermontUnWersity Park, Pennsylvania 16802 Burlington, Vermont 05401

Dr. M. Kenney Professor R. DragoDepartment of Chemistry Department of ChemistryCase Western University University of FloridaCleveland, Ohio 44106 Gainesville, Florida 32611

Dr. R. Lenz Dr. D. L. VenezkyDepartment of Chemistry Code 6130University of Massachusetts Naval Research LaboratoryAmherst, Massachusetts 01002 Washington, D.C. 20375

Dr. M. David Curtis Professor T. KatzDepartment of Chemistry Department of ChemistryUniversity of Michigan Columbia UniversityAnn Arbor, Michigan 48105 New York, New York 10027

NASA-Lewis Research Center Professor James ChienAttn: Dr. T. T. Serafini, MS 49-1 Department of Chemistry21000 Brookpark Road University of MassachusettsCleveland, Ohio 44135 Anterst, Massachusetts 01002

Dr. J. Griffith Professor J. SalamoneNaval Research Laboratory Department of ChemistryChemistry Section, Code 6120 University of LowellWashington, D.C. 20375 Lowell, Massachusetts 01854

Professor G. Wnek Dr. S. CooperDepartment of Materials Science Department of Chemistry

and Engineering University of WisconsinMassachusetts Institute of Technology 750 University AvenueCambridge, Massachusetts 02139 Madison, Wisconsin 53706

0L/413/83/01356B/413-2

TECHNICAL REPORT DISTRIBUTION LIST, 356B

Professor 0. Grubb Professor H. HallDepartment of Materials Science Department of Chemistry

and Engineering University of ArizonaCornell University Tucson, Arizona 85721Ithaca, New York 14853

Professor T. Marks Professor G. WhitesidesDepartment of Chemistry Department of ChemistryNorthwestern University Harvard UniversityEvanston, Illinois 60201 Cambridge, Massachusetts 02138

Professor C. Chung Professor H. IshidaDepartment of Materials Engineering Department of Macromolecular ScienceRensselaer Polytechnic Institute Case Western UniversityTroy, New York 12181 Cleveland, Ohio 44106

Professor Malcolm B. Polk Dr. K. PaciorekDepartment of Chemistry Ultrasystems, Inc.Atlanta University P.O. Box 19605Atlanta, Georgia 30314 Irvine, California 92715

Dr. D. B. Cotts Professor 0. SeyferthSRI International Department of Chemistry333 Ravenswood Avenue Massachusetts Institute of TechnologyMenlo Park, California 94205 Cambridge, Massachusetts 02139

Dr. Kurt Baum Dr. G. Bryan StreetFluorochem, Inc. IBM Research Laboratory, K32/281680 S. Ayon Avenue San Jose, California 95193Azuza, California 91702

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