Inorg. Chem. 1988, 27. 2709-2714 Table V. Force Field of CF?OSF' CF' 6.15 CF'/CP C.~ P 5.49 CF5/CF7 5.75 CF6)CF7 C F' 5.36 CF'/CO co 4.19 C F 6 / C 0 os 4.48 C F 7 / C 0 SF 2.30 CO/F5CF6 F'CP 2.20 CO/F5CF7 F5CF7 1.79 CO/ F6CF7 F8CF7 1.77 CF5/F5CF6 F~CO 1.09 CF5/F5CF7 F6co 0.81 CF5/F6CF7 F~CO 1.79 CP/F5CF6 cos 1.27 CF6/ F6CF7 OSF FCOS (torsion) 0.10 FSCO (torsion) 0.21
1.55 1.36 1.15 0.69 0.86 0.75 -0.81 -0.56 -0.41 0.61 0.59 -0.23 0.47 0.14
CP/F'CF7 -0.62 CF7/F%2F7 0.65 CF7)F5CF7 0.39 CF7/F'Cp -0.44 0.68 CO/COS 0.60 CO/OS OS/SF 0.50 0.31 OS/OSF 0.24 SF/OSF COS/OSF 0.72 0.35 OS/COS
Force constants in lo2 N/m; bending force constants and bendingstretching constants normalized on m.
Table 111, vibrational frequencies and isotopic shifts from Table IV, and the program N C A ~ 'were used. The final result is shown in Table V, and the calculated frequencies and isotopic shifts are listed in Table IV. Because the vibrational couplings are very strong in this molecule, it was not possible to get a satisfying agreement between observed and calculated frequencies. Nevertheless, the results are reasonable for the proposed C F 3 0 S F structure. 2. W Photolysis of CFS(0)F in the Gas Phase and in CD2Clz Solution. Photolysis of CF3S(0)F in a quartz glass bulb at 10-100 (21) Christen, D. J. Mol. Struct. 1978, 48, 101.
2709
mbar and 20 OC,or diluted in CDzClzat -80 OC in an NMR tube, does not generate CF30SF. The molecules COFz, SOFz, CF3SSCF3, and CzF6in various ratios could be detected by IR and I9F NMR spectroscopy. Conclusion The compound C F 3 0 S F is formed by UV photolysis of matrix-isolated trifluoromethanesulfinyl fluoride, CF3S(0)F. In contrast to the photoisomerization of SzFz6or SezFz,22there is no stationary equilibrium between the isomers of CF,S(O)F. By prolonged UV irradiation, it decomposed to COF2 and SFz. C F 3 0 S F is the first known fluorosulfenyl ester. It was not possible to synthesize it on a preparative scale by gas-phase or solution photolysis. Likely primary photolysis products are CF3 and O S F radicals, which may recombine in the matrix cage to CF30SF, but in the gas phase or in solution they can diffuse and form other more stable products. For the fluorosulfenyl trifluoromethyl ester 13 of 15 possible fundamental vibrations were measured and assigned. Data were also obtained for the I3C- and '*O-enriched species, enabling us to deduce a reliable structure and force field for this unusual molecule. Acknowledgment. Support by the Deutsche Forschungsgemeinschaft and Fonds der Chemischen Industrie is gratefully acknowledged. Registry No. CF3S(0)F, 812-12-4; CF30SF, 115095-67-5; CF3SF3, 374-10-7; I3CF3S(O)F, 115095-68-6; CF3S(I80)F, 115095-69-7; CF,"S(O)F, 115095-70-0; I3CF3OSF, 115095-71-1; CF3I8OSF, 115095-72-2; CF3034SF, 115095-73-3. (22) Haas, A.; Willner, H.2.Anorg. Allg. Chem. 1979, 454, 17.
Contribution from the Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712
Anionic Perphosphido and Perarsenido Complexes of Gallium and Indium Carl J. Carrano, Alan H. Cowley,* Dean M. Giolando, Richard A. Jones,* Christine M. Nunn, and John M. Power Received April 7, 1987 Reaction of 4 equiv of LiEPh2 with MC13 in T H F at -78 OC yields the anionic perphosphido and perarsenido complexes [Li(THF),] [M(EPhZ),] (1, M = Ga, E = P 2, M = In, E = P 3, M = Ga, E = As) in 70-80% yields. The air-sensitive complexes are yellow and crystalline and can be recrystallized from THF/toluene mixtures. The X-ray structures of 1-3 have been determined. The anionic moieties of 1-3 are very similar. The M-E bond lengths, EPhz geometries, and M(EC2)4conformations are indicative of M-E single bonding in each case. Crystal data for 1: C64H72GaLi04P4, M,= 1105.84, orthorhombic, P212121(No. 19), a = 13.945 (7) A, 6 = 18.332 ( 5 ) A, c = 23.671 (4) A, V = 6051.7 (3) A), Dald = 1.214 g cm-), Z = 4, p(Mo Ka) = 5.99 cm-'. Refinement of 4127 reflections (I > 341)) out of 4155 unique observed reflections (3O I 20 I 44O) gave R and R, values of 0.0688 and 0.0747, respective1 Crystal data for 2 C64H721nLi04P4, orthorhombic, P212121(No. 19), a = 14.017 (4) A, 6 = 18.402 (9) A, c = 23.696 (5) V = 6112.6 (9) A', Dcplcd= 1.251 g ern-), Z = 4, ~ ( M Ka) o = 5.25 cm-'. Refinement of 4163 reflections (I > 3u(I)) out of 4189 unique observed reflections (3' I 20 5 44') gave R and R, values of 0.0558 and 0.0644, respectively. Crystal data for 3: CssH8&s4GaLiO5, triclinic, Pi (No. 2), a = 13.392 (7) A, 6 = 13.521 ( 5 ) A, c = 19.025 (7) A, a = 87.92 (3)O, @ = 76.19 (4)O, y = 83.16 (3)O, V = 3321.1 (7) A), Dald = 1.354 g ~ m - Z~ ,= 2, p(Mo Ka) = 24.30 cm-l. Refinement of 8132 reflections (3O 5 20 5 44O) gave R and R, values of 0.0626 and 0.0707, respectively. There is a disordered T H F molecule not bound to Li in the structure of 3.
1;
Over 20 years ago, Coates, Beachley, and co-workers pioneered the svnthesis of comwunds featuring bonding between the heavier group 13 and 15 eiements.' Such compounds have attracted recent attention2v3because of their potential utility as percursors t o compound semiconductor materials such as gallium arsenide and indium phosphide. Gallium-arsenic and indium-phosphorus compounds have now been characterized in which two or three phosphorus- or arsenic-containing groups are directly bonded to (1) See, for example: Coates, G. E.;Graham, J. J. Chem. Soc. 1963,233. Beachley, 0.T.;Coates, G. E. J. Chem. SOC.1965, 3241.
0020-1669/88/1327-2709$01,50/0
the group 1 3 element.2*3 However, to t h e best of our knowledge, no compounds are known in which the gallium or indium to (2) (a) Wells, R. L.; M y , A. P.;McPhail, A. T.; Pitt, C. G. J. Chem. Sa., Chem. Commun. 1986,487. (b) Arif, A. M.; Benac, B. L.; Cowley, A. H.;Geerts, R.; Jones, R. A.; Kidd, K. B.; Power, J. M.; Schwab, S.T. J. Chem. Soc., Chem. Commun. 1986,1543. (c) Pitt, C. G.; Purdy, A. P.; Higa, K.T.; Wells, R. L. Organometallics 1986, 5, 1266. (d) Pitt, C. G.; Higa, K. T.; McPhail, A. T.; Wells, R. L. Inorg. Chem. 1986, 25, 2483. (e) Wells, R. L.; Purdy, A. P.; McPhail, A. T.; Pitt, C. G. J . Organomet. Chem. 1986, 308, 281. (3) Bradley, D. C., personal communication. We are indebted to Professor Bradley for his courtesy in providing structral data prior to publication.
0 1988 American Chemical Society
Carrano et al.
2710 Inorganic Chemistry, Vol. 27, No. 15, 1988 Table 1. Crystal Structure Parameters for Complexes 1-3 2
3
Description of Crystal yellow rhombohedral 0.40 X 0.40 X 0.30
yellow rhombohedral 0.35 X 0.40 X 0.30
yellow rhombohedral 0.45 X 0.35 X 0.35
Unit Cell orthorhombic P2,2,2, (No. 19)
orthorhombic P2,2,2, (No. 19)
triclinic pi (NO.2)
14.017 18.402 23.696 90 90 90 6112.6
13.392 (7) 13.521 ( 5 ) 19.025 (7) 87.92 (3) 76.19 (4) 83.16 (3)
1
Color habit max cryst dimens. mm
cryst syst space group unit cell params
13.945 (7) 18.332 ( 5 ) 23.671 (4) 90 90 90 6051.7 (3) 4 CaH,,GaLiP,O, 1105.84 1.214 5.99
a, A
b, A e,
A
a. deg
8. des Y. deg
v,A3
molecules per unit cell formula mol wt calcd density, g cm-’ ~(calcd),cm-’
(4) (9) (5)
(9)
4
Data Collection radiation (A, A) scan technique scan width, deg range of indices hkl 28 range, deg no. of reflns measd std reflns intens orientation decay of stds, % min transmission, % max transmission. % av transmission, % agrement factor for averaged reflns
F. intens
no. of reflns used (I > 3 4 ) ) no. of params varied data/parameter ratio shift/error ratio esd of an ObseNn of unit wt R’ ‘.R
Table 11. Selected Bond Lengths (A) [U(THF),I[Ga(PPh2),l (1)’ Ga-PI 2.434 (6) Ga-P2 2.399 (7) Ga-P3 2.419 (7) Ga-P4 2.386 (7) PI-c11 1.90 (2) PI-C2I 1.84 (2) P2-C3 I 1.86 (2) P2-C41 1.87 (2) PICa-P2 PICa-P3 PIGa-P4 PZCaeP3 P2Ca-P4 P36a-P4 Ga-PI-C11 G~-PI-CZI CII-PI-C2I Ga-P2-C31 Ga-P2-C41 C31-P2-C41
100.5 (2)
99.7 (2) 112.3 (3) 111.9 (2) 115.5
(2)
114.9 (2) 106.2 17) i 1 1 . 0(7j 103 ( I ) 103 2 (7) 105.2 (7) 108 ( I )
Mo Ka (0.71073) +14, +19, +25 4155
8/28 0.80 + 0.35 (tan 8) +14, +19..+25 3 5 28 5 44 4189
+14, +l4, +20 8565
(305). (303)
94.35 99.87 97.65
(154). (136) 13.7 90.56 99.81 95.94
65.65 99.41 82.38
not averaged not averaged
not averaged not averaged
0.028 0.036
Structure Determination 4127 4163 557 567 7.41 7.34 1.551 1.334 4.270 4.510 0.0688 0.0558 0.0747 0.0644
8132 594 13.69 1.272 ~
~~~
4.272 0.0626 0.0707
and Bond Angles (deg) for P3-C51 P3q61 P4-C71 P4-C81 01-Li 02-Li 03-Li 04-Li Ga-P3-C51 Ga-P3
