JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (Rane i U. 5. Patent OMe) (D Conyreb, 158, dy th America Ct JANUARY 11, 1958 Vows 80 Nowser 1 PHYSICAL AND INORGANIC CHEMISTRY [Cowtemertox vRox THe Dupaeruenr op CkEMISTRY oF Tit UsiVERSttY oF MrcsiGA] ‘The Preparation and Properties of Heramminecobalt(II1) Borohydride, ‘Hexamminechromium II) Borohydride and Ammonium Borohydride® By R, W, Parry, D. R Scuuttz ano P. R. Girarpor ‘Recewveo Novestees 3, 1058, Metheds for the preparation of hesamminesobalt( III) borohydride, hexamminechromisma(IIT) borchydride and ax saonivm boone ate testbed. Hexamimineehromitm( TTL) bowser im ard ammonisan borok yd Sompoutd decomposes at 25° under high vac iin stable compound up to BO, se cobalt ‘unstable above 208. ‘The thermal de Somposiion of these compounds, as wel as thls decomposition In aqueous solation has een stediee, ‘The synthesis of penetration-type metal ammine borohydrides may be achieved by metathesis reactions in liquid ammonia of the general type 1. NH MME,+ «NaBH, a NaF + MHD, This reaction has been effected for those cases which M is the hexamminechromitim(ITI) ion, the hexamminecobalt({11) ion and the ammonium ion. ‘The resulting new compounds, heramminechro- ‘ium (IE) borohydride! and hexamminecobalt(I!1) borohydride, are described herein, Although am- monium borohydride was mentioned brielly by Armstrong’ ina. previously classified industrial report, litte information on its properties was avail- able. "In astudy of the “Giammontate of diborane” the properties of this compound and of the metal ammine salts became important, and_a more thorough investigetion wes warranted. From the academic stanipeint ammonium borohydride is intreaing ince it represents boreycidie ald Experimental A. Materils.—1. The best grade of commercially ayal- able reagent Was deed and ased except as Byted bel Conumertil, NaBH was recyetalizel twice from gud 2. Hexammisecobalt(II1) Fluoride.—Fresily precipi taged Ago was ound Wit hetamaiecobeltCH) Enoate (2) AerjetBagavering Cory, Dna Reyrt No. 2, Janeary26, fort be. tna cold wortar (0"). The wolde were fltered of ‘aud the trate and washings Were newtralzed with HF (DE Placed in vacua deicestor over concentrated HSOy AAG? ait ene ope pcre rich formed wer filtered om ® sstered giis iit, wacked with a very mal Sect of ld de ce fechate al ‘onal. The prosuct wae ried over The serena of he frodict india the presence of the [CaUNif)"** lon and an analysis eave: Coo anos. Neb, 8.8%" Fog Caiculated values for (Cot NHs)iFs are: SBS Rh 18, Since [Ca(S eter wile the eat scutin, ou eas afte i tation {0 prevent bifuoride contamination. nee EST A REE ra peal rat ene ad a ee terre 0, ICe(sttjalch + 88g? E> (CH(NHA)ITs + B44C1 fn AgF solution, prepared from AgiO and 6 N HF, died earfaly too tion sontining 0,004 sole of en Tminectromung(ilt) chiride. After" string of sl {he lear sclution (OH 82) ce flaced dm a Vatuurn deo {or over coneeatraied sulfuric acid, ‘The ervstls which ore in'n wack were Stersd on a sintered glace fi with iciusbn. of mois air ani. dried over MAOH nal Gated for (CrNHp Be 'P, 27.05 Cy, 3.882 Ni, 8 28.05; HE, 0.06." Fouad: Gr, 2i.l; Nit, 470; tree He, 10. "the analysis sugzests slight contamination with the bidvionde sale 'B. General Procedure for the Metathesis Reacton.— sie atte eon cde card ot yd 1M 'SifShiometrie cmeunes of the appropente dry tue