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Ms< 3A43 35340 CUSSIFIMTON C W a M Oho73sa 3A43 1 A £«v> t .My Thie docuarat consists of Jg> pages " Ro. _J} of 2hk copies, 8eries A* ♦ * D*te of Xseue: Kay ?f 19SX R eport fustoer: K-T05 Subject Category: CBBGSTHf^aBBBRAL 4 /0 - . 35340 * . ';: #Ms< gBBfcOBl IliLllliN COMPLEXES • 'SI, John T. Barr and Charles A. Horton Work Supervised by R. H. Lafferty, Jr. Laboratory Diriilon F. V. Hurd, Superintendent CUSSIFIMTON c w a m Sr ATOMIC *■•?«Snrt.i-.wt QW «.oH —*Q " \uiur. nwOMSirioATION HRAMCS F *-. CARBIDE ABB CARBOH CHSKXCALB CtMPAI* K-25 P lan t Oak Bldge, Tennessee RESTRICTS) This document contains rpsgSCS^^atB ae defined in the Atonic Energy Act traneaittal or the disclosure of ita dSSteSta in any manner to an unauthorised person is prohibited. t $ g * ' jf-V §a.*v OHO 73sa ***• v* * i Report Sodwr: K-705 Subject Category: cmCBm-CBBORAL Date of leant: m y 7, 1951 T itle : Uimon-TOB URAHUM COttUDOS Author: J. T. Birr and c. A. Horton ABSTRACT Bight chelated uranium complexes and 7 uranium amines, prepared fraft the reaction of organic aolutlone of uranium ealta with complexlng agents and organic bases, respectively, have been prepared and characterised. Salicylic and lactic acids, acetylacetone, and similar ccmplaxing agents which contain only acidic functional group*, shoved little reaction with uraniua compounds In organic solutions. However, upon the addition of an external base to the solution of the uraniua compound and the com­ pleting agent, the formation of a Werner-type Caspian resulted. For example, uranyl n itra te hexahydrate, sa lic y lic a d d , and pyridine in butyl acetate solution gave a precipitate of aallcylatoaquopyridlnouranyl n itra te . Uranium(IV) chloride, la c tic a d d and pyridine formed dichloro- dllactatodipyridinouraaiua(IV) • I-Phenylglydne and quinaldlnlc add, which contain both anlno and carboxylic groups, reacted readily with uraniua compounds In organic solution. With quinaldlnlc acid, uranyl nitrats hexahydrate precipitated dlqulnaldlnatodlaquouranyl. Uraniun(IV) chloride reacted with B- pbenylglyclne in butyl acetate solution to precipitate dlchloroblt - (R"phenylglyclnato)H-pbenylglyclnouraniua(I7), which upon recrystallitatlon from aqueous solution gave bls(R*phenylglyclnato)tetraaquouranlwi(n) chloride. Pyridine precipitated aquopyridinoumayl nitrate from organic solutions of uranyl nitrate hexahydrate, and trlpyrldinodluranium(If) chloride from solutions of uranium(IY) chloride. Aniline formed diaaillnoureniun(IY) chloride with uraniua(IV) chloride. ? The infrared spectra of 10 of the complexes were determined in the 2 to 15 micron range, from which it was found that the amino nitrogen atoms were bound directly to the uranium atom by a coordinate-covalent linkage. In all complexes which contained pyridine, the characteristic pyridine iiiii'n'i'iiii'iV i 'r absorption bands a t 2.76, 5*02, 5*20, 5»*t6> and 5*93/1 were missing, llev ... absorption bands in the 11.2-12.0 and 15.0-13.2 j l regions appeared to be due to the RC00-U linkage. ' It was postulated that, in organic solutions, a preliminary attack by a basic group upon the uranium stem of an un-lonlttd molecule was necessary before chelation could occur. Step-wise replacement of inorganic anions by complexlng agents could then proceed u n til the maximal coordination number of the uraniua atom was attained. * * mmsi-vm mmm mm*m Darlas the court* of a recent — arch for specific chelating astute for u m vith solution* of urtniun caapousds In organic solvent* (5), It ate found that the — type conplejdng agsnte which have been reported to be useful for the detection of uranium in afueoua solution* reacted with uraniun compounds in organic solvent** It wte Observed, however, that non/ of the product* which were for— i In noo-**— ous eolation differed greatly fron thoee foe— d in a*— ou* — die* Opon farther investigation, It we* found that the— product* were Vernar-typt cunple— s, rather than the in— r-ccnple* type of ccnpound which la fox— d to readily by ureal— . theoretical Disc— loa The concept of secondary, or coordinate, valence w— introduced by War— r to account for the fox— tloa of — tal and— compounds la which — dn or or— ale — 1— • — re thought to be bound to a — talllc ion by a coordinate- covalent sharing of — electron pair furnished by the nitrogen etc*. This theory was developed fron a study of the anlnocobaltlchlorld*s, who— structures are eh— 11 below* ♦ ♦ h 3 % ✓ "h3 ♦ MJN\ ✓ " Hs hjN*♦ CO •*-MKs MjK ”♦ CO ♦'Cl ter . „/• V.. V... Eenanlnocobalt(XIZ) Chloride Chloropsnto— inocobalt(nz) Chloride ""1 + T 5 * /Cl Co MJ*^ f ^ Cl ^ n h 3 . id ■ Dlchlorotet— dnocobalt(xn) Chloride It woe later found that other groups canid fans similar compounds. 8c— of the acre familiar of the— ore shown below. •*“■**•# t v. g| .-mm. ***«**-"■' W**»*MIW Wr -4Mt« WWW 7 «■» Ml S ” -u Ms*\ /c« Cu Pt ccr CM''* Ns* Cl'* ^Cl Potassium Tetracyaneto- Trlrhlnm— laoyUtlnai(I?) ccpperata(II) Chloride T 1 “ i : H C 8 n ^ ^SCM Cl^ ^C« 2No HO HC8^ ^MCM m Ml Sodiiaa Tetraisothlocyanato- J)ichlorodiaminoplatim»( 1Z) mercuryate(Il) These Verner-type, or penetration, complexes contain inorganic anions, and art characterised by the fact that one or both of the Ions are complex, being formed by coordinate-coTalant bonds* Many solvated aolecules may be Included in this class. With the exception of a few neutral compounds similar to dlchlorodlsimni noplat lnum( 11), these complexes are more soluble in vater than in non-polar solvents, have high melting points, and behave as typical electrolytes in solution. This idea vas later developed by Bilge!ck and Pauling to explain the formation of chelate compounds, "oniua" ions and hydrogen bonds, and is a fundamental part of the Levis acid-base theory. According to these later-workers, such bonds occur by the interaction of an electron-donor (electrophobic groups such aa trlvalent nitrogen, carbonyl and hydroxyl oxygen, and sulfide sulfur) vith an acceptor group. The acceptance of a pair of electrons then results in the completion or expansion of an electron shell in the acceptor, or in the formation of a nev electron grouping* The number of donor groups which msy associate themselves vith an acceptor le a function of the spatial requirements of the donor groups, and of the amount of expansion possible in the electronic configuration of the acceptor. For moat metallic lone this number le a characteristic constant knovn as the coordination number (C. I.), and varies from 2 to 8 as the' ionic radius of the metal increases. * a The coordinating groups are arranged in a definite epatial arrangeaent in the voluae around the central ton. This voluat la known as the coordination »ph*r«. Polyfunctlocal organic ccaplexlng agents any fora 5- or 6-Mehbered ring! with Metallic Iona If the functional groups art in the proper positions. These complexes are known at chelate coapounds. Xxaaplta with ethylene* dlaalns and oxalic add are given below. These reagent* are bldentate (two points of attachaent) coeplexing agent*. ♦ CHt - W*“ CM. / o*c*o ter »r Pt av„_ , " - CHf 0»C-0"* \>-C»0 lie (ethyleaedt ail nn) plat lnua( II) Potassiua Dioxalatoplatinate(n) Chloride If one coordinate valance and one ionic valance are used to font the ring structure, the resulting compound is terand an Inner coaplex. If the coordination maker of the Metallic Ion it twice the ionic charge, and a bldentate reagent is used, the resulting compound le an inner ccaplex of the first order. These compounds are non-electrolytes and possess ■any covalent properties, such as low Melting points, Halted volatility, high solubility in organic solvents, and low solubility in water. If the coordination maber of the ion le greater than twice the ionic charge, additional coordinating groups any attach theMaelvea to the central loo to coMplete the coordination maber. Bxaaplee of these are given below. OeC-0^ yO-CeO „ o r \ ♦ Pt H S » W \ 0 U Dlglyclnatoplatlnua(Xl) DiacetylacetonoAlpyridinoiron( XI) C.I. « twice ton charge C.H. greater than twice ion charge Hletorlcal Bedew A few uraolua compounds have been described in the literature which nay have been Werner-type coaplexes; however, this structure has not beun definitely assigned to any previously reported coepound. Faecal (25) reported the exists nee of several cyanouranatee and Hauser (lk) and Xaghilleri and Qorl (16) prepared a mabar of oxalato coapounde which r».« i 9 may have bid complex-loo structure. P i m i d i (6,9,10,11) reported a m i tel of uranyl compounds vith ortho-di phenols which be termed beteropoly aclde, but vhich also may be considered u Vernsr-type complexes. Andrew (9) peppered a complex naLatouranyl salt, but the ionic charge of the complex anion uni due to aa uncoordinated carboxyl group rather than to a reiidual charge of a coordinated function. This it probably true of may of the complex ureayl anion* found in aqueous solutions of the polyfunctional aliphatic aclde, tuch as citric, tartaric, and ascorbic aclde (3b), at ordinary hydrogen ion concentrations. Much non work has been done on the uranium amines. Rasc&nu reviewed the literature up to 1930 (&7)» and described the preparation and properties of mny more conpoundi (98-31), Including such pyrldlno compounds as •quopyridino- and dlpyrldlnouranyl chloride and nitrate, and the antipyrlM, pbenacltln, and ’oyrlmidon analogs • Vllkle-Dorfurt and Schllepbake (b2) prepared the pentaaatlpyrlnouranyl perchlorate, and Inghlllerl and Oori (16,17) reported a serlee of anllino end quiallino salts, although their Interpretation of the structure• were obviously wrong in several instances. Lloyd and Cities (21) described an addition compound between hexmethylenetetrmlne and uranyl acetate. Koatlgnle (23) prepared a series of amines frcn heterocyclic anines. Spacu (36) described a series of amonlatee of uranyl and uranlua(IV) chlorides, nost of which vere stable only at low texperstures.
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