ADA3' 2241 SYNTHESIS OF PHOSPHORUS NITROGEN P0 YMFRS USING , NV /RFAGEN S. U) rEXAS CHRISTIAN UNIV FORT WORT DEPT fEiM S RY P WISIAN NfItSON ET At 22 NOV 83

M 0''i It CUODC/ 30 RRO N0004-79 CO0632 F67 N

U in mis

MICROCOPY RESCLU'tT1O4W CHAR

4 #

r * **4tool 5~

OFT£CE OF MAVL USAR

Contract No. NOOOA4-79-C-0632

Task No. NR 053-720

TECHNICAL REPORT NO. TCU/DCITRL-83-04

I

Synthesis of Phosphorus-Nitrogen Polymers

Using Si-N-P Reagents

by

Patty Wisima--eilson, h.oop K. Roy,

Ze-mun Xle, and Robert H. Neilson

Prepared for Publication

ACS Symosium Series, No. 232

DTIC

Tema Cbzlstim VLblwrelty C~"Dept. of CkmSstry

Fort Worth, IM min

3.v+e 22, 116Pau=1 Is seemet thu at.6d son"s @twom

M 4e hue us~psWIT

WECUftITY CLUAikfi0a OF TIS PAG& ("hen boo. Eam. ________________

REPORT DOCUMENTATION PAGENURSERla -= r CEUNN

TCUIDCITI-83-04 ;1____3__________x__ V_

4. TITLE (ME SuN.) S. Type or RepoRtt 6 PEi~fOD cOvCAZO

Synthesis of Phosphorus.Nitroge Rprt18Polymers Using Si-N-P Reagents ______________

41. PERFORMING ORg. REPORT NUMOeER

TR-83-04 E7. AUTHORfO) Ik. CONTRACT OR GRANT NUMBERI'a

P. Wisian-Neilson, A. K. Roy, N01-9C031-Z.-M. Xie, and R.U. Neilson N01-9C03

9. PER1FORNMING ORGANIZATION NAME AND ADDRESS1 £P" .OR UI MMK

Teas Christian University NR-053-720Fort Worth, TX 763.29

It. 'CONTROLLING OFFICE MANEt AND ADDRESS It. REPORT DATE

November 22, 1983Office of Naval Research Ii. NUNDER OF PAGES

914.MONTORNG GENY NMEG ADDRESS(U dIIemt k Cm&fkW Off..) IS. 8ECURITY CLASS (W1 We Nom

Ise. ' ASSICATIONDOW"GRADI"GI IS. DISTRIOUTIO0N STATEMENT (of MIN& Atwat)

Approved for public release; distribution unlimited

17. DISTRISUTION STATEMEN0T We. .Mo abobse w L.h SO. 20 afeMmt km Pw

Prepared for Publication in ACS Bimposium Series, No. 23 *@SssOm 16'

IS. SUPPLEMNTARY MOTES

P-N Polymer ft

(Silylaftuophospbiaes Phoephease ido

2L AMSEYA j8=hu 92~ 04 it amP 26 1S

so procure@ds to vazimas oligame end polymeric -Nsystems. For oxm3.e,

p*2y(diaUky ph-peme,(3W 3 are readiy obtatmed vft the thesel

ind Sa am"-- rieto of corta 3-etlylptwepbialaia

OD M so ~ I 4.0Aoo o~awwwww~m o

/loo

SRCUUY 'CLASIICAYION OF TIS PAE S Sh kemWO

)naddition. novel 3-coordinate phosphorus-V compomds including the bis(in)

phosphoran&es, Rp(-NSIM/jY 2 , can potefitially lead to new polymers of formla.

Or%,the phosphorus analogs of electrically conducting n*The synthesis

of lyphosphazenes and their precursors and the syntheis otential pre-

c s6rs to are discusre

... ... ..

'

'

00S

I. .....

i0t

1' ~ ~ ~ ~ ~ SNRZI OF -- . S-- -- --- -- 2 ----- -- -G_ _

-OYMR USIN -- i--- ---- N

Patt wfiusoloAro . oznZa

Pobtt R. iNeilson, xo .Ry emnle

Department of ChemistryTexas Christian UniversityTort Vorth, Texas 76129

readily obtained via the thermal-. condestion-polymerization of certain* U-silYlphosphiuisins". Xe3SiiNfP(%)R 2. In

addition, novel 3-coordinate phosphorus-V- - compounds including the bis(iniso')-

phaosphorenes, I?('uNSi~e3)2, canpotentially lead to new polymers offormula (APY)n. the phosphorus analogs ofelectrically conducting (91)s. Thesynthesis of polyphosphaseses and theirprecursors and the synthesis of potential

-- -precursors to (RI5)n are discussed.

The structural and chemical diversity of compounds4containing the li-U-P linkage is a result of both the

variety of coordinatioa sumbers wbich phesphoretsmayeaum as&7:~ the resistivity of the BI-* hoed. The

combsoton f tkeee featurs gIT** Si-U-? eememuads*very premising sstheotic stliy, rartitulaorly is the

area of isergasie Velymer orst~vois.Typisally. the **et asess paeomrseta to nov

* The difeseetoae eheweato*I aef the ape*Ade, wbich is'as* to the sueloopklZis site at pheepkevas 4w4 acempleneatary *eootoopiis *is* at *iliest nab*# them,very vematiLe reeseste fter howe be*s sed Is a saw

*systhesis of ethyl 46itr *,eart substitated phespha--sese (as1u) 5 Q.) -64 a hed. to :2k. Pteparetie ofPre*siis Pvefoesto s.o in.Iye etialseu4sets peleystema ot Sewel tormua (tIPi)U.

-- >M. MR

~~1 1V 7 -

PI

Synthesis of Polyphospbaseaes

rWork in the polymer synthesis area has beenenhanced by a convenient "one-pot" synthesis which wasdeveloped by J.C. Wilburn (2) (eq 1). Yields of thephospbines prepared in this sanner are typically 60 to

.(3Si)2Nl

-" I) n-]luLlj(1? ) idC3

11.351 'e

L[ (M.3 Si) 21?C123 1)

or iii (N3S1)2V1"

to 902 and quantities of 250 to 300 grams are easilyobtained. The use of PhPC1 2 i place of PC13 allows

2-_for the introduction of pbenyl/alkyl substitution atphosphorus.

many simple oxidation reactions of tertiary alkyl.' or aryl phosphizes are less straightforward in

phosphines with silylamino substituents (3-8). Twosuch reactions have resulted in precursors tophospbatenes. The first of these is the reaction of

:' broine with disubstituted sily1ominophosphimes (7) to26 give e33ilt and P-brouo-M-silylphosphinimiaea (eq 2).

At 2

(Me3Si)2X-P 'e$8 put.lR- (2

a A £2o It, lb, A0403, 4",

i ~lSl~e$, C€i~m0UoII . etc.

The pbe.pbLsfmLeso ire thermally sattable and readily !olminaoe Mollift at eaperatu'ee of treater thas 1006C'to gets eall eli. pboseaeb... (eq S)e (Q)

will

r 0..'" " ' ... -'i.' -, ' :4 ,.

R R

M*3 SilmP-Bv-*MGrS (3).

Is ~ I'RK R3,4

More importantly, the P-brouopbospbinimines reactsmOOthly with C73CE201 in the presence Of Et3 N to formP(trifluoroethozy)phosphiniuines (eq 4) (7). On heat-Ing in either sealed glass ampoules or a stainless

R RCF3 C1201

* )f 3SiN-P-Br ib MSSSiV-P-0C12C13 (4)- - -- It 3 1*

steel bomb these phosphinimines readily eliminateN0M3 SiOC12 CF3 (eq 5) and form. excluuively polymericphoophazenes. (.1)

Me3 SiV0?-OCIICF3 P* ]?I3F M63SiOCI2CFP3 (5)

R No. It ph- ph ph

at UXj ItI so~ It 0*Thes physical properties of tbkso polymers varyconsiderably as the substituetet at'phosphorus arechanged. ?.ydmtyp.pue)(VoiP*)s Is a Ahltef .flu-fori polyvar with a welght avoraeA mlecular

*weight (1,) . $@,00So Asomizod,. by ligut seattur-LOS1m. It is soluble is CRIClg, CaCl3. C2S$UgOS. asd

* TRY20 as& ba* a melting #*int olf 1580C end & glasstesties, t..pee4tAWe of -42*0 (1). The Ai*thyl deal*#

(ztg2u)s' e the other hand, is ut* Pouplexiag aimees* its virtual is...L~ lity is all aseoto 9*0e04*0 oo et

eharacteuisotiou otber them *1inned suaM~le.Is **street to the aihyl sbstituted polymeors, the

P-Pbayl af*06p,6nd, Ift(Ke )nlan 004,Ctt(20) 5 , are*brittle, broe eolerod *stas wikare le

soluble is MY * air* m4*& flossatd by tr*..emest~of solwest. sttw mta s eosrwih

zv,

by Sel permeation chromatography for [Ph(Ne)sindicates rd to be 54,000. Its &lass transitiontemperature was found to be 370C.

Phosphasene copolymers have also 'beeu prepared bythe thermolysis of equisolar mixtures of thephenyl/alkyl and dialkyl substituted ?-trifluoroethoxy-phosphinimines.

Ph RII

R *me, it

These materials are generally more elastomeric cud-rubbesr-like in-appearance than either of the corres-*ponding homopolymers. Such systems indicate that it: should be possible to "custom design" polyphosphazenesby choosing precursors with desirable substituents.

- In summary, this new and general method of synthe--sizing both cyclic and -polymeric phosphasenes (eq 6)

R R

NG 3 Si*P-1 -* U 3SiI P {?3 (6)

RN

-involves properly designed U-silylpbosphisimines which-contain a leaving Sroup X and the desired substituentsI and RI on phosphorus. Such compounds eliminatesubstituted silons Mo55i1 and forp cyclic or polymeric

*--phosphacenes. When I is St or, as reported earlierT.) IP oly small ring compounds ae formed, but when

I is C73S2@. polymeric Vb-4*besanea result. Incontrast to the nsal& uetbeds of Vrprearing ineratipolymers via riog epeoing pOLyWV t oao, this .4s anunusual oxampto of's a *aditi eeosp* tymariatien *blchgives as inorganic P-W polymr backtbone. Ibis method,thoerer boo Vbhe Ovmta~a 49 41lwive- the- initialeosnwtrwti.. * e*1 soal I*ml boil*LS bianka whichineorpovate toolribtb #tat agrouf. 1bo Ispurtieslarfy Useful fts t: prrawt~t.. Of olkyI andloraryl substitued P*1yobhtbsoooae with diret Carbon to,phoporo boods, a system %blob Is difficult to

achiee by tev stoC.

. . . .. .. . . ...... l D U", J11

cC1 4 . aactions of (SiIylamiso),bospbines

Other l-silylphospbinimines vhich are alsosuitably constructed phosphasene precursors, tau beprepared by a second oxidation reaction of silylanino-phosphines. When these phosphines react with carbontetrachloride, two types of P-cblorophosphiminines maybe formed by essentially two pathvays (eq 7) (8).

It

I-C-S i% 3"-cRc13 I

M03SiV0mP-R'

Cl/C21 CC14(7)

(M* 3Si) 2y-P R I' I

I-C-u-MS3SiCC13i. ,

Cl.- Siej3, Ne, Ph, 31' - C 2SiXe3 , Ne, It, i-Pr, t-Su, Ph, Xu02, Oft,

OC12CF3

__ The elimination of CdC1 3 as shown in pathway Aoccurs in similar systems vhich contain a C-i moiety ato phosphorus. Presumably$ initial formation of an ion

- pair intermediate (11P C1)(CC13 " ) (jj) is followed byattack of the CCl 3 "ion at the bytogen on the acarbon with elimination of C2Cl3 ,&iwing ylide products(eq 8) (lU.12). lovever. in systems which

ft 1 I'

* 2--t C2#l*0 r. j-c~ Ioll (6

U €li ci¢

contaim a ai1ylmawl. .*b.ttq.., thae eea,s yii4ee

a re 1weertAlSy LaStwudOt. a~wb rteaS wie o11" -slky *igt (eq. 9) 4o a t-* ~ ~ ~ ~ ~ ~ bH 'ib*eb~pfLLneee s Lapatha7 A.

CU -- Sl. (9)

Cl C

An alternate pathway is possible for systemscontaining silylamino substituents at phosphorus. Thismost likely involves attack Of the CC13 - anion at theelectrophilic silicon resulting in elimination oflle3SiCCl3 as shown in pathway S. In the systemsinvestigated thus far, the reaction pathway preference

-~appears to be influenced by: (1) solvent polarity, and()steric and electronic effects of the substituents

at phosphorus (8).

Low-coordinate Phosphorus System*

Regardless of which I-silylphosphinimine products-are formed they all are potential precursors to-phoophatenes via elimination Of Me3SiCl- Preliminary

-- evidence indicates that the thermal elimination does*indeed occur in *soe cases. The N-silylphoophinimines7-are also potential precursor* to another type of novelSi-I-P compound, i.e. three-coordinate phoophoranes:

I-?F 4-01 3- 1 0 -

£ CIRi, at

Our imterest in such compound$ stems mainly fromthe possibility that theoy might be useful precursor. tonew classes of pbe#VkorV.-c0mtaimfia; polymers or cyelicoligasets. 14"o-t . likagoo such *a 3 *f usixe3 of

-CRISL3 could serve so site$ for comdeaeatibm-polyser-isatiem reeetiess, lesting to *ovel cyclic or polymericsystem.,

wbort I N or Si'1. 1%*** material* r aw eeoleetremicofth the slecawiolp ***testis$ polymer, Poly(omlfmr

)s4

................ .......- -.I". - y

p of ne t t fla li It. I Snr' t

salt ~bat~n ~tli~ttrisat * bs$S*)1 (eq* 10).Is the tat whre to Le geutyrnim, bne h

-.. .u .RL~j .t .ee .R(StAflbv)

*s (31p St)9.7)-j fa,*n a .tste at ltk* -ootoa bi' oro

p *[1.lli -eas

i(wq

411-(11

* 3 Si Has

(WC3Si) 2N-P\ I 1CHi~

Mee$

Me IMe 3SiNinP C-SiM*3 145 0c #HiC

CXRCiS'Me3

000M WSONe

14.-k CR2 i4e

M0I CSiMe 3

and Ne3 SiCl and formation of a white crystalline solidwhich has been identified as the aehln substituted4-neabered P-U- P-U ring syte 63 ' +22.2). Upondistillation (b.p. 91-92000.01 an), the monomerHes?(UvSiKe3)(jCUSiK*3) was collected as a colorlessliquid S+1 2.12.7). Th. monomer reverts to the diner

*on standing at room temperature overnight. It readilyadds methanol across the POC bona'to form the ?-methozy

*phosphinisine. iOn hoating at 1450C for two hours, both the

monomer and diujyT form a novel 4-membered P-I-1P-C ringsIFcompound. Tke F1P spectrum *f thij compeund cousists

of two doublets of equal 1kassity at S~O' and 8-10.6with Jos a 15.3 Is. 'The, downfield shift coerrelateswith thajt Of tepebrm .the ria system

conainng ei1Sicit 8*0st.4ts. *hit* the urfieldShift is gist ar to that *9 the 4-mabered ring systemse

I'containing N*S3 Si*' *stitette at uas ee. Theriags hbe" *I** "mies SUSwCOtOTISed 1#b coi 1Vl

* leatel aualysis, "A moltlar weight seaserememts**Lang both mals spectrestopy end cryoseerse tohaiqes.

Ptelisimauy studies Isdicate that the reactions ofsoae of these diners with XPCd2 result in elinisation

.. .-.... . . . . . . . . . . . . .. . . . . . . .

of e3 i a ring opening reactions. Details ofthese investigations and complete characterization ofthese ring systems will be reported elsewhere.

Acknowledsments

The authors thank the U.S. Army Research Office,the U.S. Office of Naval Research, and the Robert A.Welch Foundation for generous financial support.

Literature Cited

* 1. Wisian-Neilson, P., Neilson, R.1. J. Am. Chem. Soc.1980, 102, 2848.

- 2. Neilson, R.N.; Wisian-Neilson, P. Inorg. Chem.1982, 21, 3568.

- 3. Wilburn, J.C.; Neilson, R. H. Inorl. Chem. 1977,16, 2519.

4. Wilburn, J.C.; Neilson, R.E. InorZ. Chem. 1979, 18,347.

- 5. Neilson, R.N.; Wisian-Neilson, P.; Wilburn, J.C.Inorg. Chem. 1980, 19, 413.

6. Wilburn, J.C.; Wisian-Neilson, P.; Neilson, R.E.Inorg. Choi. 1979, 18, 1429.

7. Wisian-loIilson, P.; Neilson, R.E. Inor&. Chem.: .1980, 19, 1875.

- 8. Li, B.-L.; Eugenito, J.S. Jr.; Neilson, R.E.;Wisian-Neilson, P. Ij!.s. Chem., in press.

-- 9. Wisian-Neilson, P.; Neilson, R.E.; Cowley, A.B.-- Inors. Chem. 1977, 16, 1460.-. 10. Appel, R. Anew. Chem. Int. Ed. Engl. 1975, 14,-. 801.- 11. Appel, R.; Peters, J.; Schnitz, R. Z. Anorg. All.

" Chem. 1981, 18, 475.- 12. Koodiashnyi, 0.1. Tetrahedron Lett. 1980, 21,

3983.13. Xie, Z.-M.; Neilson, i.E. Oganouetallics, in press.14. Scherer, O.J.; Kuhn, • Cbeu o 197&, 107, 2123.I,

J,