1064 NOTES
Inorganic Chemistry
the same stability and are in reasonable agreement with the results of previous investigators (Table IV). T h e present investigation, however, does not give supporting evidence for the existence of the CdFz species previously suggested with a formation constant p2 = 3.4.l The irreversibility of the reduction waves of Ni(II), Co(II), Cr(III), and Ti(II1) prevented application of the method to these ions. Acknowledgrnents.-M-e are indebted to the International Atomic Energy Agency for a fellowship for $tefica hLesari6, 1960-1961, and to the United States Atomic Energy Commission for partial support under Contract AT(30-1) -905.
any compounds which might be capable of formation with the help of radiation are unstable to either the radiation or the slightly elevated temperatures prevailing during the experiments. The use of ionizing radiation provides a new approach to the study of the mechanics of the xenon-fluorine reaction. Due to the large number of primary processes involved in the radiation-induced reaction, one would not expect it to follow the same course as the photochemical reaction. Indeed the latter yields only XeF2, regardless of the initial xenon-fluorine ratio.2 Further work is being done to determine the effect on product composition of varying the xenonfluorine ratio in the radiation-induced reaction.
Acknowledgment.-We wish to acknowledge the assistance of F. W. Bloch and W. D. Riel in carrying out the experiments with xenon and chlorine and xenon CONTRIBUTION FROM THE BROOKHAVEN KATIONAL and oxygen. LABORATORY, UPTOIT,NEWYORK (2) J. L. Weeks, C. L. Chernick, a n d 32. S. I f a t h e s o n , zbzd., 84, 4612 (1962).
Compound Formation by ?-Irradiation of Xenon-Fluorine Mixtures BY DOSALDR. MACKESZIEAND RICHARD H. x71SWALL,
JR.
Received March 26. 1963
Mixtures of X e and Fz in slightly greater than 2 :1 mole ratio of F2 to Xe were exposed, in prefluorinated nickel containers, to high-intensity ?-radiation from Co60 sources. The pressure was observed to fall, as i t would if the two elements combined, and a solid product was later obtained from the container, by sublimation. This resembled the product of the thermal reaction carried out according to the procedure of Claassen, et ul.,I both in appearance and chemical behavior. Analysis of the solid obtained from one of the irradiations was carried out by hydrolyzing a weighed sample in NaOH solution and determining fluoride in the solution. Results of the analysis indicated a composition XeFa.o, suggesting a mixture of difluoride and tetrafluoride. For a given composition it is possible to calculate a radiation yield from the pressure drop and other parameters of the experiment. Conditions of the experiment were as follows: initial F2/Xe ratio, 2.6; initial pressure, 18.6 p.s.i.g.; volume of container, 330 cc. ; temperature, 64' ; length of irradiation, 130 hr.; 4P,-6.0p.s.i.; dose rate (to Fricke dosimeter), 4.0 X l o 6 rads/hr. Calculation gives a G-value for consumption of X e of 3.4 atoms per 100 e.v. absorbed in the gas mixture. The fact that radiation brings about fluorination of xenon suggests its use in the synthesis of other rare gas compounds. Several such experiments have been tried. Mixtures of krypton and fluorine, xenon and chlorine, and xenon and oxygen were irradiated in the Gamma Facility, and a mixture of xenon and oxygen was irradiated in the Brookhaven graphite reactor. No compounds were observed in any case. Apparently (1) H. H. Claassen, H.Selig, a n d J. G. Malm, J. A m . Chem. Sac., 84, 3593 (1QRZ).
COSTRIBUTION FROM THE DEPARTMEKT OF CHEMISTRY, OF TECHXOLOGY, CLEVELAND, OHIO CASEINSTITUTE
Octahedral Silicon-Oxygen, GermaniumOxygen, and Tin-Oxygen Bond Lengths from Interplanar Spacings in the Phthalocyanino Polymers (PcSiO),, (PcGeO),, and (PcSnO),l BYWILLIAM J. KROESKE,LAURELE. SUTTON, RALPHD. JOYNER,ASD MALCOLM E. KENSEY
Received A p d 13, 1963
I n the search for inorganic oligomers and polymers in this Laboratory, attention has been given to phthalocyanino rings linked together by metal-oxygen chains, ie., PcA410A1Pc, PcA10Si(Pc)OA41Pc, PcAlOSi(Pc)OSi (Pc)OAlPc, HOSi (Pc)OSi (Pc)OH, (PcSiO),, and (PcGeO),.2 Both the phthalocyanino rings and the groups I11 and IV metal-oxygen chains used in these have the advantage of being inherently stable. I n addition the use of the bonding positions of the metal rather than those of the benzene rings of the chelate for polymerization gives stable links between the monomer units. I n the complexes formed in this way the symmetrical ring system is unsubstituted and thus unweakened by pendant groups on the benzene rings and the chain is stabilized because the metal in it is in a high coordination number and because the whole chain is encased by the ring. Further work has now established that another member of this series, (PcSnO),, can be prepared by the (1) Support for this work came both from Kational Science Foundation G r a n t NSF-Gt6833 a n d from Air Force Office of Scientific Research Contract AF 49(688)-773. I t is based on portions of t h e Ph.D. thesis of William J . Kroenke. P c = the phthalocyanino ligand. (2) R. D. Joyner a n d M. E. Kenney, J . A m . Chem. Soc., 82, 5790 (1960): J. E. Owen and hl. E. Kenney, Inovg. Chem., 1, 334 (1962); R . 11. Joyner and hl. E, Kanney, ibid., 1, 717 (1862),
VoZ, 2, No. 5, October, 1963
NOTES 1065
thermal vacuum dehydration of the new compound, rings are parallel and the chain is linear the octahedral P c S ~ ( O H ) ~It. ~also has been found that (PcGeO), Sn-0 bond length is 1.91 f 0.02 8. The Sn-0 bond can be prepared by the usual vacuum dehydration length is reported to be 1.93-1.98 8. in S ~ ( O H ) B ~ - . ~ technique. The nature of the Si, Gel and Sn longIt is interesting to note t h a t even a t the separation of chain polymers has been determined by means of 3.83 8.the rings are still parallel. studies based on elemental analysis, infrared spectra, An experiment has verified the assignment of these thermogravimetric analysis, and resistance to chemical intense d-spacings. A sample of (PcGeO), was heatattack. In general (PcSiO), is quite stable chemically, treated for 2.5 hr. a t 500” under high vacuum. The (PcGeO), less stable, and (PcSnO), relatively unstable; infrared spectrum of the residue was identical with the for example, (PcSiO), is unaffected by aqueous H F a t spectrum of the starting material except t h a t the ablooo, aqueous 2 M NaOH a t reflux, and &So4 a t room sorption band resulting from the unsymmetrical temperature, while (PcGeO), withstands only the stretching vibration of the Ge-0-Ge group shifted NaOH and (PcSnO), does not withstand even the from 864 t o 899 cm.-l. X-Ray powder photographs NaOH. revealed that the sample became more crystalline. The A feature of all these systems is that the great planar strongest X-ray line corresponded to a spacing of 3.48 phthalocyanino ring predetermines the over-all stereok0.02 .&. and the second-order reflection of this spacing chemistry, forcing the tetravalent metals into octaheto a value of twice 1.738 0.003 8. A simple picture dral coordination, the aluminum into square pyramidal that accounts for these phenomena is t h a t an ordering coordination, and the chains into a truly linear arof the polymer took place accompanied by a contracrangement. In the case of the polymers a further tion of the Ge-0-Ge distance and an increase in the feature of these stereochemically locked systems is that Ge-0 bond strength. These data imply t h a t the the size of the planar phthalocyanino ring simplifies the polymer units have special preferred orientation. interpretation of the X-ray powder patterns sufficiently Acknowledgment.-The authors wish to acknowledge so t h a t definite structural information can be obtained. a helpful conversation with Drs. M. J. Hunter and X-Ray powder photographs of (PcSiO), reveal that A. J. Barry of Dow-Corning. the strongest reflection corresponds to an interplanar spacing of 3.32 k 0.02 8. The value of the spacing calculated from the second-order reflection is twice 1.659 f 0.003 A. The interplanar spacing of 3.32 8. JOINT CONTRIBUTION FROM THE INSTITUT FUR ANORGANISCHE is attributed to the repeat distance of the polymer chain CHEMIE,TECHNISCHE HOCHSCHULE, STUTTGART, GERMANY, and if this is correct it follows directly t h a t the adjaTHE DEPARTMENTS OF CHEMISTRY, DUKEUNIVERSITY, cent phthalocyanino rings are stacked parallel in a DURHAM,NORTHCAROLINA, AND THE UNIVERSITY “deck of cards” fashion. Because the oxygens are OF FLORIDA, GAINESVILLE, FLORIDA, A N D THE U. S. ARMY RESEARCHOFFICE, DURHAM, wedged between eight nitrogens i t seems highly imNORTHCAROLINA probable t h a t the SiOSi bond angle deviates from 180”. Therefore the value of 1.66 A. must correspond The Structure of to the octahedral Si-0 bond length. For comparison (Methylpheny1amino)-methylphenylborane i t may be noted that ordinary tetrahedral Si-0 bonds are in a range near 1.64 As4 BY HANSBAECHLE,’~ HERYANN J. B E C H E R , ~ ~ X-Ray powder photographs of (PcGeO), are very HASSO BEYER,’~ WALLACE S. BREY, J R . , ~JOHN ~ W. D A W S O N , ~ ~ similar to those obtained for (PcSiO),. Here the MARTIN E. FULLER, II,lCAND KURTL \ T ~ ~ ~ ~ ~ ~ ~ l b s l d strongest reflection corresponds to a spacing of 3.50 f 0.02 8. The value calculated from the secondReceived January 14,1963 order reflection is twice 1.746 & 0.003 8. The The existence of double bond character for the boron3.50 8.spacing is assigned to the repeat distance of nitrogen linkage of aminoboranes has long been adthe polymer chain and i t is concluded that the rings vocated by Wiberg.2 Recently, unsymmetrically subare again stacked parallel. This interpretation gives stituted aminoboranes have become available and, an octahedral Ge-0 bond length of 1.75 8. The based primarily on physicochemical constants, a sugreported average tetrahedral Ge-0 bond lengths gestion has been made that such compounds may in (GeOa)2-are 1.84-1.86 exhibit cis-trans i s o m e r i ~ m . ~Two recent short comThe X-ray data for (PcSnO), are similar to those for munications on the proton magnetic resonance spectra (PcSiO), and (PcGeO), although the pattern is more of two selected aminoboranes, substituted unsymdiffuse. An intense line occurs corresponding to a metrically a t either the boron4 or the nitrogen5 a t o p , spacing of 3.83 f 0.03 A. This is attributable to the repeat distance in the polymer chain. The value of (1) (a) Technische Hochschule, S t u t t g a r t ; (b) Duke University; (c) this spacing based on the second-order reflection is University of Florida; (d) U. S.Army Research Office. (2) E. Wiberg, Naturwissenschaffen, 85, 182 (1948). twice 1.91 0.02 A. Again concluding that the
*
*
(3) W. J. Kroenke and 31. E. Kenney, Inoug. Chem., i n press. ( 4 ) L. E. S u t t o n , “Interatomic Distances,” The Chemical Society, London. 1968, pp, AM%-41.
(3) K. Niedenzu and J. W. Dawson, J . A m . Chem. SOL, 8 3 , 4223 (1960). (4) G. E. Ryschkewitsch, W. S. Brey, Jr., a n d A. Saji, ibid., 83, 1010 (1961). ( 5 ) P. A. Barfield, M. F. Lappert, and J. Lee, Proc. Chem. Soc., 4 2 1 (1961).
