2260
NOTES
Inouyunic Chemistry
Separation of (CH3)2NBH2from B2He.[ (CH3)2N]4B2.-The 1: 1 products that differ from those expected from the preadduct (1.30 mmoles) prepared in t h e above manner was washed viously reported reaction of HBBCOand waterR several times with fresh portions of 2-methylbutane. Precau1000 tions mere taken t o keep t h e temperature of t h e system a t or H3BCO 3H20 +B(OH)a 3Hz CO (1 1 below -78". T h e white solids which remained on t h e filter frit decomposed into a white volatile solid a n d a viscous nonvolatile The purpose of this work is to elucidate the reactions liquid on warming t o -23". T h e solid was sublimed away from that occur between H3BCO and water. t h e liquid at room temperature and was identified as (CH3)2XBH2 (1.11 mmoles) by its vapor-phase infrared spectrum. Experimental Section T h u s t h e (CH:,)2r\TBH2:B2H6.[(CH,)zN]4B2 rat0 is 0.86:l. I n a Standard vacuum procedures and T apparatus were usccl second experiment 2.27 mmoles of (CH3)zNBHz was isolated throughout. from t h e decomposition of 1.95 mmoles of t h e 1: 1 adduct giving a Materials.-Diborane4 and potassium boranocarbonate' were ( C H ~ ) ~ X ' B H Z : B ~[ H (C OH . ~ ) Z N ratio ] ~ B ~of 1.17: 1. prepared b y previously published procedures. I n t h e preparation Attempted Isolation of Stable, Monomeric, B-B Bonded Speof potassium boranocarbonate t h e carbon monoxide was passed cies.-In a n a t t e m p t t o prepare a stable trimethylamine derivathrough a n aqueous sodium hydroxide solution t o remove any tive of t h e fragment remaining after t h e 1 : 1 adduct had lost 1 carbon dioxide present and then three -78" traps to remove mole of (CHB)&BHZ,a n excess of t h e Lewis base was added t o water. T h e carbon monoxide borane used in these experiments t h e adduct and t h e mixture was allowed t o stand at -23". From was generated as needed by t h e action of 85y0 phosphoric acid on this mixture only a trace of a substance which might b e a monoan appropriate amount of t h e boranocarbonate.] meric B-B bonded species was detected. Most of t h e fragment T h e Reaction of Gaseous H 3 B C 0 and Water.--X 20.1111 quailformed a nonvolatile liquid which slowly converted t o a yellow t i t y of water in a 100-ml round.bottomed flask equipped with a glass. vacuum adapter was evacuated. T h e flask and contents were Since hydride-dimethylamino exchange occurred in t h e reacthen cooled t o -196" and 1.00 mmole of H 3 B C 0 was contion of B2H6 and [(CH3)2SI1B2, an a t t e m p t was made to syndensed into t h e flask. T h e stopcock on t h e adapter was closed thesize NaB3Hs by allowing a large excess of S a B H j and B2H6 and t h e system was kept at 0" for 2 days. After t h a t time the t o react with a dilute tetrahydrofuran solution of [ ( C H ~ ) Z N ] ~ B ~contents . volatile at room temperature were passed through a t r a p KO chemical evidence for the presence of [BaHg]- was found in a t -78" and two at -196". T h e noncondensable gases were this reaction mixture. measured b y a Toepler pump system. An infrared spectrum of
+
Acknowledgments.-This work was supported in part by the Research Corporation and the National Science Foundation under GP-204. J. D. C. wishes to thank NASA for a predoctoral fellowship.
The Hydrolysis of Carbon Monoxide Borane B Y LEO J. MALONE ASD 51. I
