230 J. N. KEITH,I. J. SOI,OMON, I. SHEFT,ANI) H.H. HYMAN 90-957,. vents.
Inorgnnic ChPmisfry
B ~ [ N ( C H ~ ) ~ ] ~ ( SisB soluble C ~ H ~ )in most organic sol-
9. B ~ [ ( N C H ~ ) ~ C Z H ~ ] Z .(5.38 - B ~ Cmmoles) ~~ and 25 nil of CHzCla were distilled into a reaction vessel containing syniAnal. Calcd for CeH~6NaB2S?: C, 35.68; H, 7.Y9; S,13.87; dixnethylethylenediamine (21.6 mmoles) a t - 196". Reaction B, 10.71; S, 31.75; mol wt, 201.98. Found: C, 35.34; H , was allowed to take place over a temperature range of -78 to 7.98; K , 13.74; B, 10.50; mol wt, 219 (0.040 m ) and 236 25" for 17 hr, resulting in the formation of a white precipitate. (0.064 m ) in benzene. Base hydrolysis gave 0.98 mole of hyAfter distilling away the CHnC12, extraction of the residue with drogen per mole of B z [ N ( C H ~ ) ~ ] ~ ( S ~ C ~ H ~ ) . benzene followed by pumping away the benzene afforded a white X-Ray powder diffraction pattern data, d (relative intensity): crystalline solid (mp 45-47'). An identical product (shown by 7.69 (m), 6.68 (vs), 6.05 (m), 5.56 (vs), 5.01 (m), 4.18 (s), 4.00 X-ray powder diffraction data) was prepared by the transaniitxa(m), 3.83 (s), 3.58 (vs), 3.36 (vs), 3.17 (m), 2.468 (vw), 2.404 4 with syiiz-diniethylethylenediamine; lit. tion of B~[N(CHS)S] (vw), 2.292 (vw), 2.161 (vw), 2.113 (vw), 1.965 (vw), 1.920 mp 43-44", bp 85' (5 mm).z This compound is soluble in the (vw), 1.823 (w). common organic solvents. Infrared spectrum (KBr, cm-I): 3106 (w),2907 (s), 2786 Anal. Calcd for C ~ H Q ~ S ~C,B 49.55; L: H, 10.40; IT,28.89; (m), 1508 (sh), 1495 (m), 1450 (m), 1449 (m), 1404 (m), 1381 B, 11.16; mol wt, 193.92. Found: C, 49.31; H, 10.22; B, (s), 1284 (s), 1266 (s), 1198 (m), 1136 (m), 1110 (s), 1055 (vw), 11.02. 1012 (m), 993 (m), 897 (s), 801 (vm), 767 (vm), 676 (m), 571 X-Ray powder diffraction pattern data, d (relative intensity): 8.46 (vs), 7.25 (s), 6.44 (vs), 4.86 (s), 4.37 (s), 4.22 (s), 4.02 8. B2(SeC?H&[NH(CH3)2] n.-B2[N(CH3)2] 4 (4.3 mmoles) and (s), 3.83 (m), 3.75 (m), 3.61 (vs), 3.51 (s), 3.38 (m), 3.21 (vw), HSCHyCHaSH (9.2 mmoles) were mixed together in a closed sys2.641 (VU'), 2.468 (w),2.386 (vm), 2.049 (vw), 1.796 (vw). tem without solvent. The mixture was agitated and allowed to Infrared spectrum (KBr, cm-1): 2950 (m),2849 (s), 2809 equilibrate a t room temperature. Crystals slowly began to form (s), 2762 (m), 1486 (m), 1470 (w),1435 (m), 1426 ( i n ) , 1397 at the interface of the liquid mixture and the glass walls of the (sh), 1387 (s), 1264 (s), 1199 (s), 1059 (s), 971 (w),648 (w), 038 reaction vessel. The reaction mixture was allowed to stand over(m), 624 (w), 543 (w),526 (w),519 (w). night, yielding a pinkish solid plus excess HSCHXHLSH. 10. Be[ (NH)f&H4]z.-This compound was prepared by a Recrystallization of this solid from a benzeiie-pentane solution procedure reported elsewhere through the traxisaminatiou of afforded a white crystalline product. It is soluble in common B2[S(CH3)2]4 with phenylenediamine in a 1 : 2 molar r a t i ~ . ~ , ' ~ organic solvents and appears to be stable with respect to evoluThis compound showed good thermal and hydrolytic stability. tion of NH(CH&. Its low solubility in common organic solvents precluded Anal. Calcd for C8HP2KSB2S4: C, 32.44; H, 7.49; N, 9.46; molecular weight determinations. Attempts to prepare this B, 7.31; S, 43.31; mol wt, 296.22. Found: C, 32.26; H, compound through the reaction of B2C14with o-phenylenediamine 7.33; B, 7.13; mol wt, 285 (0.012 9%) in benzene. Base hydrolyyielded impure material which could not be successfully purified. sis gave 0.86 mole of hydrogen per mole of B L ( S P C ~ H ~ ) ~ . ~ N HAnal. Calcd for C I Z H ~ ~ N C, ~ B61.63; ~: H, 5.17; N, 23.95; B, 9.25; mol wt, 233.86. Found: C, 61.39; H, 4.96; B, 9.31. (CH8)z. X-Ray powder diffraction pattern data, d (relative intensity): X-Ray powder diffraction pattern data, d (relative intensity): 8.93 (m), 7.53 (s), 6.84 (vs), 5.74 (vs), 5.37 (w),4.98 (m), 4.28 12.03 (vs), 6.61 (m), 6.05 (m), 4.44 (vs), 3.93 (m), 3.78 (w), (s), 3.98 (w),3.65 (m), 3.39 (vw), 3.18 (w), 3.02 (w), 2.931 3.63 (s), 3.32 (m), 3.17 (m), 3.07 (s), 3.02 (s), 2.826 (w),2.637 (m), 2.849 (w),2.780 (vw), 2.698 (vw), 2.629 (vw), 2.417 (vw), (TY), 1.821 (w),1.726 (vw). 2.312 ( w ) . Infrared spectrum (KBr, cm-l): 3425 (w), 3344 (m), 1608 (w), Infrared spectrum (KBr, cm-'): 2994( m), 2915 (s), 2762 (m), 1592 (m), 1510 (m), 1495 (sh), 1477 (s), 1399 (w),1319 (s), 2421 (m), 1464 (s), 1418 (w),1266 (s), 1222 (sh), 1132 (s), 1106 1255 (m), 1200 (vw), 1155 (m), 1044 (vw), 922 (w),909 (w), (m), 1026 (s), 948 (s), 895 (m), 799 (w),766 (vw), 693 (w),684 758 (m), 746 (s), 738 (m), 661 (m), 631 (m), 575 (w), 479 (in), 469 (vw), 426 (w). (w). (V.7).
COXTRIRUTION FROM TIT RESEARCH IXSTITUTE CHICAGO, ILLISOIS, ASD ARGOSSENATIONAL LABORATORY, XRGONSE, ILLINOIS
The Chemistry and Structure of Dioxygenyl Fluoroborate. Fluorine-18 Tracer Studies and Decomposition Kinetics BYJAMES N. KEITH, IRYIKE J. SOLOMOX, IRT'ISG SHEFT, A N D H E R B E R T H. HYMAN
Received X a y 1 , 1967 02BFa has been prepared from the reaction of BF3 with OzFz or OIFz a t low temperatures. Isotopic tracer studies of the reaction indicate that the compound is dioxygenyl fluoroborate, 02+BF4-, rather than a coordination compound, FOz+ BFI. It is suggested that 02Fis the intermediate in both the preparation and decomposition of OaBF4. The kinetic data for the thermal decomposition are consistent with the rate law dP/dt = k l K , , 2 / P ~ ~ ,T2 h. e data are explained in terms of the equilibrium OeBB(s) = OzF(g) BFa(g) and a bimolecular process for decomposition of O2F. Values for the product kiKeq2are presented for the range 0-32", from which the sum 2AH, E, is found to be 40 kcal/mole.
+
Introduction The existence of the dioxygenyl ion (02+) in dioxygenyl hexafluoroplatinatel and in the salts of the group V fluorides2 seems well established. The product of (1) N. Bartlett and D. H. Lohmann, J. Chem. Soc., 5253 (1962). (2) A. R. Young, 11, T. Hirata, and S. I. Morrow, J . A m . Ckem. Soc., 86, 20 (1064).
+
the reaction3 of OzF2 with boron trifluoride (RFs) is dioxygenyl fluoroborate (02BF4) 02Fz BFs +0zBF4 l/nFz (1)
+
+
There is no evidence t o date, however, t h a t 02BF4 ( 3 ) I. J. Solomon, R. I. Brabets, R. K. LJenishi, J. N. Keith, and J. M. Mcnonongh, Jizois. C k r i n . , 3, 467 (1064).
Vol. 7, No. 2 , February 1968
CHEMISTRY AND STRUCTURE OF DIOXYGENYI, FLUOROBORATB 231 TABLEI ANALYSISOF PRODUCTS OF 02Fz-BF3 REACTIONS Vol, cc-------,-----Decomposition---BFa F 2
I--
Ratio 0z:F%
Temp,
---Formation----BFa
0.94 0.94 0.94 1.37 1.37 1.71 1.96 1.96 1.96b 1.96
U
Fz
0 2
...
...
...
...
- 126 - 126 - 138 - 138 - 138 - 138 - 138
71.0 95.5 125.7 125.3 98.5 60.3 62.9 42.1
29.0 37.8 59.9 31.8 10.4 6.3 1.4 2.2
0.9
