PHOTOCHEMISTRY OF HALOPENTAAMMINERHODIUM(III) COMPLEXES exponential (exp) distribution. The true model is probably intermediate in nature. We examine now the relation between &,(a) and some parameters which earlier were found to correlate well. With the value of the polariaability,9 01 = 5-13 i3, for mercury, the departure of monatomic gases from the general correlation given by a plot of Po( m ) vs. 0131 (not shown; see Figure 3 in ref 4b) is emphasized. Even more dramatic is the delineation of the subclassification of inert bath gases as revealed in Figure 2. The separation of the monatomic subclass from the diat omic-linear and polyat omic-nonlinear groups is strengthened. A simple theoretical interpretation was given ea14ier.4~ The classification into three groups suggested the importance of conservation of angular momentum restrictions as a feature of the general level of efficiency. Subject to this restriction, the energy of the hot substrate entity within the collision complex was assumed t o undergo statistical redistribution with the newly formed “transition” modes (three for monatomics, and five and six, respectively, for the two other groups) of
1937
the collision complex. An increase of & ( m ) with boiling point within the D-L and P-N subclasses was interpreted as suggesting that some internal modes of the bath gas entities might play an increasingly important role in the relaxation process. However, since monatomics have no internal degrees of freedom, this rationale is not applicable t o mercury. Thus, the moderate increase in & ( a ) for mercury in Figure 2 , assumed real, could indicate some modest failure, for the noble gases, of the limiting assumption of statistical accommodation. The assumption should have enhanced validity for mercury, with its increased attractive interaction and longer life of the AHg collision complex; the collision dynamics for mercury do not differ significantly in other respects from xenon with A. It would then follow that the observed general increase with boiling point is not solely due to inof ,Bo(..) creasing participation of internal modes of the bath molecules but, to an increased efficiency, also, of their transition modes. (9) Landolt-Bornstein, “Physikalisoh-Chemische Tabellen,” Vol. 1, Part 3, Springer-Verlag, Berlin, 1951.
The Ligand Field Photochemistry of Halopentaamminerhodium (111) Complexes1 by Timm L. Kelly and John F. Endicott” Department of Chemistry, W a y n e State University, Detroit, Michigan 4820s
(Received February 7, 1972)
Publication costs assisted by T h e National Science Foundation
The irradiation of ligand field absorption bands of halopentaamminerhodium(III) complexes results in high yields of aquated products. Two different and apparently uncoupled photoaquation processes are observed : (1) halide aquation (most important for Rh(hTH3)&12+) and (2) trans-ammonia aquation (most important for Rh(NH3)d2+). The products and yields are the same for the direct and the biacetyl-sensitized excitations. Since the rhodium(II1) complexes quench the biacetyl phosphorescence, the photochemical products are attributed to reactions characteristic of ligand field excited states of triplet spin multiplicity. It is proposed that the combination of halide and trans-ammonia aquation obtained from ligand field excitation of Rh(NH3)sBr2+ results from the competitive population, decomposition, and deactivation of two different triplet states. It is further proposed that the nonradiative deactivation of these complexes involves a strong coupling mechanism and metal-ligand vibrational states.
Introduction
way of contrast, few cobalt(II1) (a 3d6metal) complexes are known to emit at any temperature and few cobaltDespite much recent interest,, careful mechanistic thinking about the photochemically reacbive ligand field excited states of transition metal complexes has (1) (a) Partial support of this research by the National Science been restricted mostly to d3 s y s t e m ~ . ~ - lThis ~ is so Foundation (Grant GP-24053) is gratefully acknowledged. (b) largely because the ligand field excited states of chroTaken in part from the Ph.D. dissertation of T . L. Kelly, Wayne State University, 1971. mium(II1) complexes are photochemically active2-I3 in ( 2 ) V. Balzani and V. Carassiti, “The Photochemistry of Coordinafluid solutions and are spectroscopically well charaction Compounds,” Academic Press, New York, N . Y . , 1970. terized in rigid media at low t e r n p e r a t u r e ~ . ~ ~ B lY ~ - ~ ~ (3) A. W. Adamson, J . Phys. Chem., 71, 798 (1967). The Journal
of
Physical Chemistry, Vol. 7 6 , -\?o, 14,2978
TIMM L. KELLY AND JOHNF. ENDICOTT
1938 (111) complexes have photoactive ligand field absorption bands.2t16s17-21 Thomas and CrosbyZ2have recently reported on the emission spectroscopy of the 4ds rhodium(II1) ammine complexes. These authors conclude that the emission observed for these complexes is phosphorescence, from the lowest energy ligand field triplet excited state (3T, 3A2, or 3E) to the 'A1 ground state. Furthermore, LIoggiz3has reported that reasonably high yields of product result from ligand field excitation of Rh(NHs)sC12+. The products in this case (1) contrast strikingly
+ h~ +Rh(NH3)50Hz3+ + C1-
Rh(NH3)6C12+
(1)
with those which we24 have observed to result from the ligand field excitation of Rh(NH3)51Z+( 2 ) . Rh(n"3)j12+
+ h~ + trans-Rh(NH3)40H2I2+
+
IL"4+
(2)
Thrse two examples serve to illustrate that the ligand field photochemistry of rhodium(II1) complexes is potentially even more varied and instructive than that of the chromium(II1) analogs. The present report relates our detailrd mechanistic studies of the ligand field photochemistry of halopentaammine complexes of rhodium(II1).
Experimental Section A. P/-eparation o j Materials and Solutions. [Rh(NH3)d21]Cl,was purchased from either Alfa Inorganics, Inc., Beverly, Mass. or Matthey-Bishop, Co., Malvern, Pa., converted to the perchlorate salt which was crystallized from dilute HC10,. Standard literature procedures were used to prepare [Rh(NH3)5Br](C104)2 from [Rh(KH3)5C1](C104)2.25The purity of the complexes after recrystallization was determined by comparison of their absorption spectra with published data. 2 6 , 2 7 tran~-Rh(NH~)~OH~Br2+. We were unable to obtain a pure crystalline sample of this complex owing to its considerable solubility (see discussion of attempted isolation of Rh(NH3)40H212+ in ref 24a). The presence of t r a n ~ - R h ( ? u " ~ ) ~ O H+~ in B r ~photolyzed solutions was confirmed by a comparison of absorption spectra with tr*ans-Rh(en)zOHzBr2+.28 Concentrations of tran~-Rh(nTH~)~OH~Br2+ were determined by converting this complex t o t~ans-Rth(r\"~)~Br~+, whose concentration could be determined spectrophotometrically (see Table I). t r a n ~ - [ R h ( N H ~ ) ? B 1 . ~ ] CAZ 0solution ~. of 0.5 g of [Rh(KHa)sBr](C104)2 in 75 ml of 0.1 M HCIO, was photolyzed at 254 nm for approximately 2 hr. About 2 g of S a B r was added to the photolyzed solution and the volume was reduced to approximately 10 ml on a steam bath. The complex was recrystallized as a bromide salt by cooling the concentrated solution in an The Journal of Physical Chemistry, Val. 76, -Yo.1.4*1978
ice bath. The complex was collected and converted to the perchlorate salt by the addition of solid XaC104 to a solution of the bromide salt in a minimum volume of warm water. Anal. Calcd for RhiY4H1204C1Br2: N, 13.0; H, 2.8; Br, 36.6. Found: K,13.1, H , 2.8; Br, 36.6. Preparation of Solutions. Solutions were prepared for photolysis using reagent grade salts and water redistilled from alkaline potassium permanganate. All solutions were deaerated, except as noted, by passing Cr2+ scrubbed S2 or argon through them before and during photolysis. The sodium perchlorate used to maintain constant ionic strength was prepared by neutralizing reagent grade anhydrous S a 2 C 0 3with reagent grade HC104. The solution was heated to remove the dissolved COZ. The concentration of the stock solution mas determined by passing an aliquot through a cation-exchange resin in the H + form and titrating the acid released with standard NaOH.
(4) H. F. Wasgestian and H. L. SchlCfer, 2.P h y s . Chem. (Frankfurt am M a i n ) , 57, 282 (1968); 62, 127 (1968). (5) P. Riccieri and H. L. Schlafer, Inorg. Chem., 9, 727 (1970). (6) R. D. Lindholm, E. Zinato, and A. W.Adamson, J . P h y s . Chem., 71, 3713 (1967); E. Zinato, R. D. Lindholm, and A. W. Adamson, J . A m e r . Chem. Soc., 91, 1076 (1969). (7) M.F. Manfrin, L. Moggi, and V. Balzani, Inorg. Chem., 10, 207 (1971).
(8) A. D. Kirk, J . A m e r . Chem. Soc., 93,283 (1971). (9) V. Balzani, R. Ballardini, M.T . Gandolfi, and L. Moggi, ibid., 93,339 (1971). (10) S. C. Pyke and R. G. Linck, ibid., 93, 5281 (1971). (11) G. B. Porter, S. M. Chen, H. L. Schlafer, and H. Gsussmann, Theoret. Chem. Acta, 20, 81 (1971). (12) E. Zinato, P. Tulli, and P. Riccieri, J . Phys. Chem., 75, 3504 (197 1). (13) C. Kutal and A. (1971).
VV. Adamson, J . A m e r . Chem.
Soc., 93, 5581
(14) G. B. Porter and H. L. Schlafer, Ber. Bunsenges. P h y s . Chem., 68, 316 (1964). (15) L. S. Forster, Transition Metal Chem., 5, 1 (1969). (16) P. D. Fleischauer and P. Fleischauer, Chem. REV.,70, 199 (1970). (17) The pentacyancobaltate(II1) complexes are exceptions in both
regards.16s's-2 (18) A. TV. Adamson, A . Chiang, and E. Zinato, J. A m e r . Chem. Soc., 91,5467 (1969). (19) G. B. Porter, ibid., 91, 3980 (1969). (20) M. Wrighton, G. S. Hammond, and H. B. Gray, ibid., 93, 5254 (1971). (21) F,Scandola and M. A. Scandola, ibid., 94, 1805 (1972). (22) T. R. Thomas and G. A. Crosby, J . MoZ. Spectrosc., 38, 118 (1971). (23) L. Moggi, Guzz. Chim. Ital., 97, 1089 (1967). (24) T. L. Kelly and J. F. Endicott, J . A m e r . Chem. Soc., 94, 1797 (1972). (25) G. U. Bushnell, G. L. Lalor, and E. A. Moelewyn-Hughes, J . Chem. Soc., A , 717 (1966). (26) C. K. Jorgensen, Acta Chem. Scand., 10, 500 (1956). (27) H. H. Sohmidtke, Z . P h y s . Chem. (Frankfurt a m Main), 45, 305 (1965). (28) H. L. Bott and A. J. Poe, J . Chem. Soc., A , 205 (1967); (b) ibid., 593 (1965).
PHOTOCHEMISTRY OF HALOPENTAAMMINERHODIUM(III) COMPLEXES
1939
Table I : Absorption Spectra of Some Rh(II1)NaXY Complexes Complex
t~ans-Rh(NHI)Jz+ tr~n~-Rh(NHa)40H212 + truns-Rh( en)& + trans-Rh(en)zOHzIZ+ t r u n ~ - R h ( N H ~ ) ~+ B r ~ t r a n ~ - R h ( N H ~ ) ~ O H +~ B r 2 trans-Rh(en)zBrz + trans-Rh( en)zOHzBr2+
Absorption maximaa
Ref
470 (333), 340 ( 1 . 9 X lo4)]270 ( 3 . 5 X lo4),222 ( 1 . 8 X lo4) 485 (185),‘ 295 (2050), 226 ( 3 . 6 X lo4) 462 (260), 340 ( 1 . 4 X lo4),269 ( 3 . 1 X lo4),222 (2 X lo4) 465 (95); 300 (1000) 438 (135), 278 (4025), 235 ( 4 . 2 X lo4) 470 sh (25),c396 (53), 370 sh (48), 235 sh (205) 425 (120), 276 (3000), 231 (-3 X lo4) -465 (20),’ ~ 3 9 (48) 5
24 24 28 28 b b 28 28
a Wavelength in nm, E, in M - 1 cm-1, given in parentheses. tration determined by conversion to dihalo complex.
* This work.
B. Analytical Procedures. Ammonia was determined by the change in pH method as described else~ h e r e . 2 ~Ammonia which was a photolysis product of Rh(NH3)5Br2+ could also be inferred when the concentration of product trans-Rh(NH3)40HzBr2+ was determined as tran~-Rh(NH3)~Br~+. For quantitative purposes this latter was accomplished by adding an aliquot of photolyte to a 0.1 M NaBr solution and heating the solution at 80” for 1hr. Halide Determinations. The concentration of any halide ion which was released during photolysis was determined potentiometrically. A method based on one developed by Shriner and Smith was used.29 Potential differences were measured using an Instrumentation Laboratory Model 145 pH meter. The mV us. ml Ag+ readings were treated in a first derivative manner.30 Separation and Identijcation of Rhodium(III) Containing Reaction Products. Ion-exchange chromatography was used to separate various cationic reaction products from the unphotolyzed starting material. Before use the column was cleaned by passing 25 ml of 2 M NaC104 through it, then washing with 100 ml of distilled water. An aliquot of photolyte was placed on a cation exchange resin column (Bio-Rad Ag 50W-X2 or X4, 200-400 mesh, Na+ form) 10 cm long and 1 cm in diameter. After the photolyte was absorbed onto the resin, the column was washed with 25 ml of distilled water. Slow elution with 0.1 M NaC104 was continued until the original band of absorbed material had separated into two or more distinct bands. The first product was removed by using 0.5 X NaC104 as the eluent. Elution was continued with 25 ml of 0.5 M NaC104, followed by 50 ml of 1M Sac104 and finally 25 ml of 2 M XaC104. The effluent was collected in 10-ml portions for spectral measurements. The charge type of all the products was determined by comparing their elution characteristics to those of other rhodium(111) ammine complexes of known charge type. The rhodium(II1) complexes in the various ion-exchange fractions were identified by comparing their uv-visible absorption spectra with those of known rhodium(II1) ammine or ethylenediamine complexes.
c
Estimated for a sample prepared in situ and concen-
C. Continuous Photolysis; Apparatus and Procedures. Photolyses were performed using a Xenon Corp., Medford, Mass., Rhdel727 Spectralirradiator in the monochromator mode. The desired wavelength region was selected using a Bausch and Lomb highintensity monochromator in combination with a RDRF2 thermophile from Charles 31. Reeder and Co., Detroit, h’Iich., and a Keithley Model 155 microvoltmeter. The monochromator-thermopile-microvoltmeter combination was also used to determine the half width of the irradiating bands. Half widths of all bands were found to be approximately 20 nm. Photolysis was performed on 3 ml of solution which was pipetted into a rectangular quartz spectrophotometer cell and Cr2+ scrubbed N2 was passed through the solution during irradiation. The solution was irradiated for a preset time period, then analyzed for products. An average rate of product formation was calculated by using product concentration and irradiation time. This average rate together with I , was used to calculate a quantum yield. Various irradiation times were used to ensure that the average rate was not a function of irradiation time. A dark sample was analyzed to check for thermal reactions for each set of photolyzed samples. The constancy of the light flux both during the course of a series of irradiations and from day to day was monitored with the RDR-F2 thermophile. The light path in the spectra irradiator was continuously flushed with X\TZ to prevent the buildup of 03 due to uv photolysis of air. Many of the 254-nm irradiations were performed using an immersion type lowpressure mercury lamp in a thermostated apparatus as described elsewhere.31 I n these determinations quantum yields were determined using the usua131photokinetic procedure : samples were irradiated for timed periods and syringes were (29) V. J. Shriner, Jr., and I f . L. Smith, A n a l . Chem., 28, 1043 (1958). (30) A . I. Vogler, “Quantitative Inorganic Analysis,” 3rd ed, Wiley, New York, N. Y . , 1961. (31) (a) J. F. Endicott and M. Z. Hoffman, J . A m e r . Chem. Soc., 87, 3348 (1965); (b) J. F. Endicott, M. Z. Hoffman, and L. S. Beres, J . P h y s . Chem., 74, 1021 (1970).
T h e Journal o f Physical Chemistry, Vol. 7 6 , S o . 14, 1972
1940 used t o withdraw samples for analysis through a Teflon needle. I n each kinetic determination the product yield was plotted as a function of irradiation time and the initial slope was compared with that of an actinometer solution of the same absorbance which had been irradiated for similar intervals. For runs at temperatures other than room temperature the reaction cell was thermostated by use of a Cary 14 constant-temperature l-cm cell holder. I n order to correct for thermal reactions a dark experiment was performed with the solution maintained at the photolysis temperature for the same length of time as the irradiated sample. D. Actinometry. The light intensity was determined by ferrioxalate actin0met1-y.~~ Owing to the high sensitivity of ferrioxalate solutions to light with A (Figure 2 ) . It is intuitively appealing to implicate the VRh-Br ; thus the experimental evidence suggests that metal-ligand stretching frequencies in the deactivation for Rh(KH3)5Cl2+the excited-state vibrational levels mechanism since even in the ground state these are low are sufficiently far apart in energy that the strong couenergy vibrations (100-500 and would be expling (Rh-X) and weak coupling (N-H) deactivation pected to be even lower in energy in an excited state mechanisms compete at room temperature. containing appreciable, localized antibonding electron I n general in this study we have found evidence that density. Thus the temperature-insensitive quantum for RhIII(NH3)jX complexes, $iSc (Figure 1) is about yields could be attributed t o the insensitivity of the unity. An exception to this may be the case of transpopulation of the implicated vibrational level t o temRh(NH3)412+ where the sensitized product yield is perature at the relatively high temperatures of the about 20% greater than the product yield from direct photochemical studies. Furthermore, excited states ligand field excitation. This would suggest that spinwith yields as high as we have observed here are conorbit coupling effects may even operate t o provide a sistent with nearly dissociative (in the case of Rhvery efficient mechanism for deexcitation of the singlet ("3) excited states t o the ground state. 5 1 + perhaps t o tally dissociative) excited states and therefore with states in which the vibrations are (52) K. Nakamoto, "Infrared Spectra of Inorganic and Coordinaexpected t o be extremely anharmonic. This feature is tion Compounds," 2nd ed, Wiley, New York, N. Y., 1970.
The Journal of Physical Chemistry, Val. 76, No. 14, 1972
