Teiichi Ito and Muraji Shibata
108 Inorganic Chemistry, Vol. 16, No. 1, 1977 60745-68-8; C ~ ( H ~ O ) S ( S C H ~ C O O H60745-69-9; )~+, Cr(H20)~ ( S C H ( C H j ) C O O H ) 2 + , 60745-70-2; ( H 2 0 ) 4 C r ( H O C H ( C H 3 ) COO)Zt, 60745-7 1-3; ( H 2 0 ) 4 C r ( H O C H 2 C 0 0 ) 2 f , 60745-72-4.
References and Notes R. H. Lane, F. A. Sedor, M. J. Gilroy. P. F. Eisenhardt, J. P. Bennett, Jr., R. X. Ewall, and L. E. Bennett, Inorg. Chem., preceding paper in this issue. R . H . Lane and L. E. Bennett, Chem. Commun., 491 (1971). (a) L,. E. Asher and E. Deutsch, Inorg. Chem., 12, 1774 (1973); (b) C. J. Weschler and E. Deutsch, ibid.,12, 2682 (1973); ( c ) L. E. Asher and E. Deutsch, ibid.,11, 2927 (1972). E. Cotte, H. Diaz, A. Miralles, and E. L. Bertha, Acta Cient. Venez., 22, 93 (1971); Chem. Abstr., 76, 20825 (1972). (a) M. V . Olson and H . Taube, Inorg. Chem., 9, 2072 (1970); (b) M. V . Olson and C. E. Behnke, ibid., 13, 1329 (1974). (a) A. A. Frost and R. G. Pearson, “Kinetics and Mechanism”, 2d ed, Wiley, Xew York, N.Y., 1961, pp 185-186; (b) R. G. Wilkins, ”The Study of Kinetics and Mechanism of Reactions of Transition Metal Complexes”, Allyn and Bacon, Boston, Mass., 1974, pp 16, 142; (c) ibid.; pp 108-1 10. R. D. Butler and H . Taube, J . A m . Chem. Soc., 87, 5597 (1965). R. E. Hamm. K. L Johnson, R. H . Perkins, and R. E. Davis, J . A m . Chem. Sac., 80, 4469 (1958). M. Ardon and H . Taube, J . Am. Chem. Soc., 89, 3661 (1967). E. Deutsch and M.Taube, Inorg. Chem., 7, 1532 (1968). (a) R. F. Childers, Jr., K. G. Vander Zyl, Jr., D. A. House, R. G. Hughes, and C. S. Garner, Inorg. Chem., 7 : 749 (1968). (b) For comparison, khyd = 2 x 10-8 s-1 can be estimated at 25 “ C for Cr(H20)s(NH2CH2CH2KH3)4+from data at higher temperatures.Ila H. B. Klonis and E. L. King, Inorg. Chem., 11, 2933 (1972). J. H. Espenson, Inorg. Chem., 8, 1554 (1969). T. W. Sivaddle and E. L. King, Inorg. Chem., 3, 234 (1964). T. W. Swaddle and E. L. King, Inorg. Chem., 4, 532 (1965). C. S. Garner and D. A. House, Transition Met. Chem., 6, 207 (1970). M. V . Olson, Inorg. Chem., 12, 1416 (1973). E. Zinato, C. Furlani, G. Lanna, and P. Riccieri, Inorg. Chem., 11, 1746 (1972). S. N. Choi and D. W . Carlyle, Inorg. Chetn., 13, 1818 (1974). K. M . Jones and J. Bjerrum, Acta Chem. Scand., 19, 974 (1965). A. Scott and H. Taube, Inorg. Chetn., 10, 62 (1971). F. Basolo and R. G . Pearson, “Mechanisms of Inorganic Reactions”, 2d ed, Wiley, New York, N.Y., 1967, p 164. C. S. Garner and D.A. House, Transition Met. Chem., 6, 187 (1970). Reference 22, p 159. (a) D, W. Kemp and E. L. King, J . A m . Chem. Soc., 89, 3433 (1967); (b) C. C. Mills, 111, and E. I,. King, ibid., 92, 3017 (1970). Reference 6b, p 203. ’I. W . Swaddle, J . A m . Chem. Soc., 89, 4338 (1967). D. K. Wakefield and W. B. Schapp, Inorg. Chem., 8, 512 (1969). F. Monacelli, Ric. Sci., 37, 777 (1967). L. R. Carey, W. E. Jones, and T. W. Swaddle, Inorx. Chem., 10, 1566 (1971). (a) For ( I - I ~ O ) S C ~ ( O O C C H ~ SKa’ H )was ~ ~ ,approximated* as 3 X from datal0 on ( H ~ O ) S C ~ ( O O C C H K, ~ ) ~can ~ . be estimated as ~ ~ s i C o l N O z l r en]ox
tutions of ligating carbonate ions in the starting complex by the desired ligands lead to the preparation of the cis&- or cis-type complex. Absorption Spectra. The absorption spectra of the cis,cis-[Co(CN)2(0-O)(NH3)2]--type complexes and the cis,cis,cis-[ C O ( C N ) ~ ( H ~ O ) ~ ( N Hcomplex ~ > ~ ] + are shown in Figure 1, in which the CD spectra are also contained as a matter of convenience. The absorption spectral data of all the dicyano complexes are summarized in Table I. The absorption spectra resemble one another; they show two peaks, or a peak and a shoulder, in the so-called first absorption band region ('TI, 'AI, region in o h parentage) and a peak, or two shoulders, in the so-called second a bsorptior! band region (' T z ~ 'A1, region in Ohparentage). Hereafter, the abbreviations Ia and Ib and I1 (or IIa and IIb) are used for the absorption maxima in both regions. In order to elucidate the Ti, band of the absorption spectra for the present [Co(CN)2(O-O)(NH3)2]--type complexes, Yamatera's treatment16 was carried out. The calculations were performed on the basis of the spectral data for some complexes: cis-[Co(CN)~(C03)2]~-,18 300 and 22 500 cm-'; cis-[Co( C N ) ~ ( O X ) ~ ]I8 ~ -800 , and 23 400 cm-l; cis-[Co(CN)2(mal)213-, 18 700 and 23 300 cm-';12 [Co(NH3)6I3+,20970 cm-'; [C0(C03)3]~-,15 500 cm-'. The calculated values are inserted in Table I. The comparison between the calculated values and the observed maxima suggests that the Ia maximum results from the first two components and the Ib maximum mainly from the third component. The absorption spectra of the other dicyano complexes could be understood similarly. By the way, the predicted positions calculated from the spectral data for the [ C O ( C N ) ~ ] ~[Co(NH3)6I3+, -, and [Co(0-O)3l3complexes were far apart from the observed maxima. Figure 2 shows crystal spectra, in the TI, region, of cis,C~S-N~[CO(CN)~CO~(NH~)~].~H~O. The polarized spectra were measured with the light polarized parallel to the crystallographic c axis (i.e., 11 c) and also with the light polarized perpendicular to the c axis (Le., c). The solution spectrum of this complex shows two peaks at 20 700 and 23 500 cm-' in the Ti, region. The unpolarized crystal spectrum also reveals apparent splitting in this region. The polarized spectra
-
-
20
25
30
35 crn-1 x
Figure 1. Absorption and CD spectra of &cis-[Co(CN),CO,(",),I(--), cis,cis,cis-[Co(CN),(H,O),(NH,),I+ (- - -), cis,cis-[Co(CN),ox(NH ,),I- (- - -), and cis&-[Co(CN),mal(NHsLI- (----). +
~~
15
25
20
30 crn-1 x
Figure 2. Crystal spectra of cis,cis-Na[Co(CN),CO3(NH3),]~ 2H,O: --, unpolarized; - -, 1 c ; --, /I c .
--
-
112 Inorganic Chemistry, Vol. 16, No. 1, 1977
Teiichi Ito and Muraji Shibata
Table 11. Absorption Spectra of the Dinitro Complexes I
CT
t n
a
-
E
Vmax
E
20.6 20.8 21.2
208 212 161
29.9 29.5 29.7
3800 3550 6630
tra~s(~~,)-[Co(NOz)z(HzO),o,I'
20.8
147
28.9
4270
cis, cis- [Co(NO,), ox(NH3),]
20.9
29.8 28.4 29.6 29.8 29.5 30.1 29.8
4290 5010 45 10 4280 4430 3570 5 120
30.1
3580
cis,cis- [ C o ( N 0 , ) ,CO,(NH,),]trans(NH,)-[ C o ( N 0 2 ) ,CO, ("3) 2 1cis,cis,cis- [ Co(NO,),(H,O),~NH,),]
+
trans(NH,)- [Co(NO 2 ) 2 OX(" ,) 2 ] &,cis- [ Co(N0,) 2mal(NH,),]trans(NH,)- [Co(NO,) ,mal(" ,) ,Icis-[Co(NO,),CO, en]cis& [ C o ( N 0 , ) ,(H,O) en]'
20.9 20.9 20.8 20.7 21.4
161 193 184 168 154 2 04 170
cis-[Co(NO,),ox(en)]'
21.1
177
~~u~s(NO,)-[CO(NO,OX(NH~)~]~21.0
a In
ir*
-
" a Vmax
Complex
a
E
Vmax
39.3 39.7 38.2 sh 42.3 37.8 43.1 39.9 38.7 40.3 39.9
19 5 0 0 15 500 18 900 10 500 1 3 700 22 5 0 0 20 2 0 0 27 6 0 0 21 9 0 0 25 2 0 0 21 000
40.0 39.7 38.2 sh 41.2 40.2
17 000 22 2 0 0
cm-' x l o 3 .
25
20
30
35 crn-1 x
IO-^
Figure 4. CD spectra of (-),,,-[Co(CN),CO,en](-), (-)589[Co(CN),(H,O),en]' (- . . -),and (+)S,,-[Co(CN),ox(en)]- (-
-
20
30
40 cm-1 x
Figure 3. Absorption spectra of cis,cis- [Co(NO,),CO,(NH,),](-), cis,cis,cis-[Co(NO,),(H,O),(NH,),]+ (- . - -),cis,cis-[Co(NO,),ox(NH,),]- (- --), and cis,cis-[Co(NO,),mal(NH,),]' 1
(- - - -).
show clear dichroism; the lower frequency band appears at 20 200 cm-l with the I c light and the higher frequency band at 24000 cm-' with the /I c axis. Again the observed peaks correspond well with the predicted positions. In the T2g band region, the spectra of the cis,cis-[Co(CN)2C03(NH3)2]- and cis- [Co(CN)2C03en]- complexes exhibit swellings at ca. 28 000 cm-l (IIa) and ca. 30000 cm-' (IIb). They perhaps originate from the split components of the T2g parentage. By comparing these IIa and IIb maxima with the observed I1 maxima of the other dicyano complexes, the I1 maxima should be recognized to be IIb maxima. The corresponding IIa maxima are not observed for complexes other than the carbonato ones. Similar phenomena have been reported for the fac(N)-[CoCN(O-O)(N)3]- l 7 and the trans- [Co( 0-0)2(py) 21 --type'* complexes. Absorption spectra of the cis,cis-[Co(N02)2(0-0)(NH3)2]--type complexes and cis,cis,cis-[Co(NO2)2(H20)2(NH3)2]+ complex are given in Figure 3 and the numerical data for all the dinitro complexes are summarized in Table 11. In the previous paper,s we communicated the characterization of the three isomers of the [Co(NO2)20x(NH3)2]- complex based on the preparative routes and the
- -).
half-widths of the first absorption bands. In the same way, the trans(NH3)- [Co(N02)2CO3(NH3)2]- and trans(NEZ3)-[Co(N02)2mal(NH3)2]complexes could be identified. As to the absorption spectra of the isomers of the dinitrodiammine complexes, the maximum of the a* a band for the cis,cis (or cis,cis,cis) isomer is at a higher frequency than that for the trans-diammine isomer. The relation of the maximum positions of the charge transfer (CT) bands between the cis,& isomer and the trans-diammine isomer is the reverse of that of the T * a bands. The spectra of the diaqua complexes, especially of the trans(NH3)-[Co(N02)2(H20)2(NH3)2]+ species, distinctly reveal two bands of the CT absorption. CD Spectra. The CD spectra of the [Co(CN)2(O-O)en]--type complexes and the [Co(CN)z(H20)2en]+ complex are shown in Figure 4. As one of the representatives of the complexes whose CD spectra reveal two apparent peaks with opposite signs, the (-)589-[Co(CN)20x(NH3)2]complex is quoted in order to discuss the CD spectrum in the TIg region. The absorption spectrum of this complex shows two maxima at 21 300 and 24 300 cm-l in the TI, region, while the CD spectrum shows two peaks at 21 200 (At = -1.44) and 24900 cm-' (A€ = +1.24). The positions predicted by Yamatera's treatment are 20 200,21500, and 24 800 cm-l. These facts suggest that the negative peak at 21 200 cm-I is the resultant of two peaks with the same signs, - and -, or the resultant of a + peak with extremely weak intensity and a minus peak with considerably strong intensity, while the positive peak at 24900 cm-' is predominantly due to the highest component at 24 800 cm-I. +-
-
Inorganic Chemistry, Vol. 16, No. I, 1977 113
cis,cis-Dicarboxylatodiammine Complexes of Co(II1)
4
+ t
I-\
/ I
+ 1.01
+ 0.5
i
I
I
I
I
\ ‘\
+2.0
\
\
\
I
I
$
+ 3.0
\
\
I n
I
\
,
,
1
20
25
30
- 1.01 - 1.01
,
,
20
25
1 30 crn-1 x
IO-^
crn-1 x
Figure 6. CD spectra of (+),,,-[Co(NO,),CO,en]-
[Co(NO,),(H,O),en]+ ((-
- -).
.-
*
IO-^
(-1,
-), and (t),,,-[Co(N03,ox(en)]-
Figure 5. CD spectra of (-),,,-[CO(NO,)~CO,(NH~~~]~ (-1, (+)~,,-[CO(NO~)~(H~O)~(NH,),I + (- . * -1, (-)589-[Co(NO32ox(NHAI- (- - -1, and (t),,,-[Co(N0,)2mal(NH,)~l- (- -1.
hypsochromically. Similar changes in the CD spectrum have been reported with the ( + ) S ~ ~ - [ C O C ~ ~ O X ( Nand H~)~](+)58g-[Co(ox)(H20)2(NH3)2]+ complexe~.~ As a result of mutual cancelation, the positive peak would shift The CD spectra of the dinitro complexes are presented in to the higher frequency side compared with the absorption Figures 5 and 6 . In these cases, too, the CD spectra are maximum. The CD spectra of the (+)58g-[Co(CN)~C03discussed in connection with split components predicted by Yamatera’s treatment; the Y N O value ~ in the TI, region was (+)S~~-[CO(CN)~(H~O)~(NH~)~I+, and (-1589(“3)21-, estimated to be 24 900 cm-l by applying the “rule of average [Co(CN)2(H20)2en] + complexes could be understood simienvironment”lg to the spectral data for the mer-[Colarly. The CD spectrum of the (+)ssg-[Co(CN)2mal(NH3)2]- (N02)3(NH3)3] complex.20 In the case of the dinitro complexes, the signs of the split components cannot be precisely complex shows two positive peaks at 20 000 (A€ = 1.02) and 24400 cm-1 (Ae = +0.68). The absorption spectrum of this defined because of narrower separations of components complex exhibits a shoulder at ca. 21 500 cm-l and a peak at compared with the separations of the dicyano complexes. For 24400 cm-’. The predicted positions of the components are the (-)58g-[Co(N02)2ox(NH3)2]complex whose CD spec20 100, 21 400, and 24 700 cm-l. By comparison of these trum exhibits a - peak at 19 500 cm-’ (Ae = -0.89) and a values it is anticipated that the CD pattern in the TI, region peak at 22300 cm-l (Ae = +1.47), the lowest component results from the three components with the -, and signs calculated to be at 19 800 cm-’ corresponds to the - peak at 19 500 cm-’ and the highest one at 21 900 cm-’ corresponds from the lower frequency side. In this case, the lower frequency CD peak (20000 cm-l) differs more from the Ia to the peak at 22 300 cm-l. The middle component at 21 000 maximum (ca. 21 500 cm-l). This fact is probably due to a cm-’ probably has a positive sign. The CD spectrum of the larger cancelation between the two closed components with (-)ssg-[Co(N02)2C03(NH3)2]complex can be interpreted similarly. The CD spectrum of the (+)58g-[Co(NO2)zmalopposite signs. Similar discussion seems to be applicable to (NH3)2]- complex results from three components with -, the (-)s8g-[Co(CN)2C03en]- complex exhibiting - and - peaks as well as the (+)58g-[Co(CN)2ox(en)]- complex exhibiting and - signs. The spectra of (+)5sg-[Co(N02)2C03en]- and -, and peaks; for the former complex three components (+)58g-[Co(N02)2ox(en)]-, each of which shows only one each with -, +, and - signs are assumed, and for the latter positive peak in the TI, region, cannot be interpreted precisely. complex three components each with -, and signs are When the (-)ssg-[Co(N02)2CO3(NH3)2]species was assumed. aquated, the CD spectrum of the resulting (+)5sg-[CoAs for the CD spectrum in the Tzg region, each of the (NOz)z(HzO)z(NH3)2] + species showed the inverse pattern to the parent carbonato complex and the peaks had extremely (-)589- [Co(CN)zox(NH3)21-, (-)5s9- [Co(CN)zCOsenl-, and (+)589-[Co(CN)zox(en)]- complexes reveals a swelling due decreased Ae values and were shifted slightly to the higher to the lowest frequency component in the Ttg region; when frequency sides. The CD spectrum of the (+)589’[CO’ the peak arising from the component has the same sign as the (NOz)z(H20)2en]+ species derived from the (+)ssg-[Cohighest frequency Component in the TI, region, the resultant (N02)2C03en]: complex, whose CD spectrum shows only one should have such a swelling. The more gentle slope in the peak with a large intensity (Ae = +2.66), gives two peaks with 28 000-30 0 0 0 - ~ m -region ~ in the CD spectrum of (-)589opposite signs and small Ae values (+0.05 and -0.27 from [Co(CN)z(HzO)zen]+ may arise from the same source. The lower frequencies). Each of these diaqua complex species CD spectrum of the (+)ssg-[Co(CN)zmal(NH3)2]shows a should have the same distribution of ligands as that of the relatively intense peak at 28 200 cm-1 (Ac = -0.48). parent carbonato complex. When the (+)~S~-[CO(CN)~C~~(NH~)~]complex is acid As is seen in the above description, alternation of a bidentate hydrolyzed, the CD spectrum of the produced diaqua complex ligand (e.g., en or C032-) by two unidentates (e.g., NH3 or +, shows the same species, (+)5gg-[Co(CN)z(H20)2(NH3)2] H2O) considerably changes their CD spectra. Thus the pattern as that for the parent carbonato complex, though the optically active complexes deriving their dissymmetry from A€ values are decreased considerably and each peak is shifted only the distribution of unidentates show characteristic difslightly to the higher frequency side, However, the acid ferences from those containing two bidentates, both in the hydrolysis of the (-)sss-[Co(CN)zC03en]- complex to give shapes of the CD spectra and in the Ae values. species makes the sign of the the (-)5g9-[Co(CN)~(H20)2en]+ Through the present work, two series of the complexes CD peak of the lowest frequency component in the TIg regjon involving carbonate, oxalate, or malonate ion have been reverse. In addition, the A€ value decreases and the peak shlfts prepared and resolved into optically active complexes. Up to
-
--
+
+
+
+,
+
+,
+,
+
+,
+
114 Inorganic Chemistry, Vol. 16, No. 1, 1977
Teiichi Ito and Muraji Shibata
Table 111. CD Spectra and Tentative Absolute Configurations Confign
-
~
18.2 (-0.02) 20.9 (+0.98) 24.1 (-1.11)
Complex
(A€)
R
S
29.7 (+0.25) 18.6 (-0.01) 21.1 (+0.17) 24.6 (-0.27)
S
R 27.3 (-0.21) 19.5 (-0.89) 22.3 (+1.47)
29.6 (t0.08) 33.9 (-0.01) 21.2 (-1.44) 24.9 ( t 1 . 2 4 )
(+Isa9- [Co(NO ),mal(NH
I-
18.3 (-0.03) 20.2 (+0.33) 22.6 (-0.34)
S
(+),,,-[Co(N0,),C03en]-
20.4 (+2.66)
R
26.3 (-0.08) 18.4 ( + 0 . 0 5 ) 22.2 (-0.27)
R
R R
27.0 sh 30.4 (+0.48) 21.1 (+0.56) 25.3 (-0.80)
31,
26.2 (-0.28)
Sb
28.2 (-0.48) 32.9 (-0.05) 20.7 (-0.86) 24.4 (- 1.46)
Rb
26.5 (-0.31)
S
27.8 sh 30.9 (-0.18) 34.5 sh 20.0 (+1.02) 24.4 (+0.68)
Confign
R
31.8 ( t o . 0 1 ) 19.3 (t0.08) 21.3 (--0.18) 24.8 ( t 1 . 4 9 )
S
27.0 sh 31.0 (-0.33)
now, several series of cobalt(II1) complexes containing these three dicarboxylato ligands have been resolved into optically active c ~ m p l e x e s . ~Every ~ - ~ ~complex of the present two series is characteristic of a rhombic chromophore. Changes in the CD spectra caused by the alternation of such dicarboxylato ligands are known to be more marked in the u-cis-[Co(OO)(edda)]--type complexes than in the s-cis- [Co(O-0)(a) (b) (edda)]--type complexes.22 It is anticipated from these facts Figure 7. Absolute configurations of (a) S(+),,,-[Co(CN),malthat the lowering in symmetry of the complex causes apparent (NHd21- and (b) R ( - ) jss-[Co(N0,),ox(NH3),1'. changes in the CD spectra. Absolute Configurations. The absolute configuration of a complex can usually be assigned by comparing the sign of a with those of these two standards. Hereafter we use the CD peak with that of the standard complex whose absolute symbols R and S for not only cis,cis complexes but also cis configuration is Such determinations of absolute complexes. configurations have been widely applied to the complexes not By comparison of the features of the CD spectra and the only with the same chromophore as that of the standard signs of the split components between the (-)589-[cO~~ complex but also with chromophores of lower ~ y m m e t r y . ~ ~ , (CN)zC03en]complex and the S(+)589-[Co(CN)2malThe complexes resolved through the present work contain three (NH3)2]- complex, it can be said that the carbonato complex kinds of ligand which are considerably separated in the is in the R configuration. The (-)589- [Co(CN)2(H20)2en]+ spectrochemical series. In such complexes, determination of species derived from this carbonato complex by acid hydrolysis the absolute configuration presents some difficulty because must have the same configuration as the parent complex, of the lack of standard complex to be compared. namely, R . Since the CD spectrum of the (+)589-[COOf the present dicyano and dinitro complexes, the absolute (CN)2CO3(NH3)2]- complex resembles that of the configurations of the (-)589- [Co(N02)20x(NH3)2]- complex R(-)~~~-[CO(CN)~(H~O)~~I-I]+ complex and has the signs -, and (+)589-[Co(CN)2mal(NH3)2]- l o complex were deter+, and -, which are inverted with respect to those for mined by x-ray analysis. The absolute configurations are S(-)589-[ Co(CN)2mal(NH3)2]-, its absolute configuration is presented in Figure 7, in which the S configuration is assigned assumed to be R . The (+)~x~-[CO(CN)~(H~O)~(NH~)~ to the (+)589-[Co(CN)2rnal(NH3)2]- complex and the R species derived from R(+)589- [ C O ( C N ) ~ C O ~ ( N H will ~ ) ~be ]configuration to the (-) 589- [Co(N02) 20x(NH3) 21- complex. in the same distribution of unidentates, namely, in R. The The nomenclature of the absolute configurations R and S (-)589-[Co(CN)20x(NH3)2]- complex will have the S confollows the rule proposed by Cahn et a1.28 figuration, because of its almost reversed CD pattern with We now presume the absolute configurations of the present and Rrespect to those of R(-)~~~-[CO(CN)Z(H~O)~~~]+ complexes by comparing their CD spectra in the TI, region (+)~~~-[CO(CN)~CO~(NH~)~]-. As to the (+)589-[CO-
Inorganic Chemistry, Vol. 16,No. 1, 1977 115
cis,cis-Dicarboxylatodiammine Complexes of Co(II1)
cis-K[Co(CN)zox(en)], 60745-77-9; cis,cis-K[Co(N02)2C03(NH3)2], (CN)2ox(en)]- complex, the anticipated CD signs are identical 6080 1-74-3; trans(NH3),cis(N02)-K [ C O ( N O ~ ) ~ C O ~ ( N H ~ ) ~ ] , complex and with those of the S(+)sgs-[Co(CN)2rnal(NH3)2]60801-75-4; cis,cis-K[Co(N02)2mal(NH3)2], 60801-76-5; cis-Kopposite to those of the R(-)sg9-[Co(CN)zCOsen]- complex, [Co(N02)2C03en], 60745-78-0; cis-K[Co(NO2)2ox(en)], 60745-79-1; and the feature of CD is reversed with respect to that for the cis,cis,cis-[Co(CN)2(H20)2(NH3)2]+, 60801-77-6; cis,cis-[CoR(-)589- [Co(CN)zCO3en]- complex; consequently, the (CN) 2( H20)zen] +, 60745-80-4; cis,cis,cis-[Co(N02)2( H 2 0 ) 2 complex is regarded as being in the S Configuration. (NH3)2]+,60801-78-7; ~ I W I ~ ( N H ~ ) - [ C O ( N O ~ ) ~ ( H ~ O ) ~ ( N H ~ ) ~ ] + , Since the CD spectrum of the (-)58g-[Co(N02)2C03(N33865-42-8; cis,cis-[Co(N02)2ox(NH3)2]-, 60762-11-0; transH3)2]- complex gives a + and a - peak from the lower fre(N~~)-[CO(NO~)~OX(NH~)~]-, 60745-81-5; tr~ns(NH3)-[C0quency side, the comparison of this CD spectrum with that (NO&ox(NH3)2]-, 60745-82-6; trans(NH3)-[Co(N02)2mal(NH3)2]-,60801-79-8; cis,cis-[Co(N02)2(H20)2en]+, 60745-83-7; of R(-)~~~‘[CO(NO~)~OX(NH~)~]gives the S configuration cis- [Co(CN)2( CO3)2] 3-, 5 1120-38-8; cis-K[ Co( C03)2(NH3)2], for this complex. The absolute configuration of the 26176-51-2; K[Co(CO3)2en], 60745-84-8; K[CoC03ox(en)], (+)s~~-[CO(NO~)~(H~O)~(NH~)~]+ species derived from 60745-85-9; ~ - ~ ~ ~ ~ - ~ C o ~ o x ~ ~ e n ~ ~ 1 ~ - ~ s s ~ - ~ C S(--)S~~-[CO(NO~)~CO~(NH~)~]can be assigned to S be60827-58-9; (-)589- [Co(ox) en)^] (+) 589- [ Co( CN)2rnal(NH3)2], cause of the retention of configuration through the ligand 60801-8 1-2; (-1589- [Co(NO2)z(en)21(-)5~9- [Co(CN)2C03enl, substitution. It will be seen from the above discussions that, 60801-83-4; (-)~~~-[C~(~~)(en)~](+)~~g-[Co(CN)~ox(en)], 60801for the dinitro complexes such as R(-)s8g-[Co(N02)20~60827-60-3; 85-6; (-)589-[Co(ox)(en)2] (-)~S~-[CO(NO~)~CO~(NH~)~]. (NH3)2]- and S(-)589- [Co(N02)2C03(NH3)2]-, treatment (-)sss-[Co(ox)(en)zl(+)sss-[Co(N02)2mal(NH3)21,60827-62-5; on the CD spectra is inverted with respect to that for the (-)~x~-[CO(NOZ)~(~~)~I(+)~S~-[CO(N~~)~CO~~~I, 60801-87-8; dicyano complexes. Since the (+)589- [Co(N02) 2mal(NH3)2](-)sss-[Co(N02)2(en)21(+)sss-[Co(N02)2ox(en)l, 60801-89-0; (+)589- [ C O ( C N ) ~ C O ~ ( N H ~ ) 60801 ~ ] - , -90-3; (+) 589-[CO( CN)2complex shows a reversed CD pattern with respect to that of (H20M~H3)21+,60801-91-4; ~ - ~ s x ~ - ~ ~ o ~ C N ~ ~ ~ H ~ O ~ z e n R(-)589-[Co(N02)2ox(NH3)2]-,the absolute configuration is 60801-92-5; (+)ss9-[Co(NO2)2(H20)2(NH3)2]+, 60801-93-6; presumed to be S . Each of the (+)ssg-[Co(N02)2CO3en]( - ) ~ x ~ - [ C O ( N ~ ~ ) ~ O X (59433-51-1; N H ~ ) ~ ] - , (+)589-[CO(N02)2and the (+)58g-[Co(N02)20x(en)]- complexes has a large (HzO)zen] +, 60801-94-7. positive peak in the TIg region. From the fact that the References and Notes dominant peaks for the S(-)~~~-[CO(NO~)~CO~(NH~)~]and C. J. Hawkins, “Absolute Configuration of Metal Complex”, Wiley, New R(--)sss-[Co(N02)20x(NH3)2]complexes have - and + signs, York, N.Y., 1971, p 7. respectively, and also from the comparison of the CD patterns I. I. Chernyaev, L. S. Korablina, and G. S. Muraveiskaya, Zh. Neorg. of these ethylenediamine complexes with those of the Khim., 10, 1045 (1965). I. I. Chernyaev, T. N. Fedotova, and 0. N. Adrianova, Zh. Neorg. Khim., R(-) 589- [Co( CN) zCO3en]- and S( +)589- [Co( CN) 2ox(en)]10, 1541 (1965). complexes, the absolute configurations of the dinitro complexes I. I. Chernyaev, T. N . Fedotova, and 0.N. Adrianova, Zh. Neorg. Khim., can be determined to be R . The (+)58g-[Co(N02)211, 1349 (1966). C. J. Hawkins, J. A. Niethe, and C. L. Wong, Chem. Commun., 427 (H20)2en]+ species derived from R(+)589-[Co(N02)2C03en](1968). should have the same distribution of ligands as that of the C. J. Hawkins, J. A. Stark, and C. L. Wong, Aust. J. Chem., 25, 273 original carbonato complex, namely, R. All of the CD spectral (1972). Y . Enomoto, T. Ito, and M. Shibata, Chem. Lett., 423 (1974). data and presumed absolute configurations are summarized T. Ito and M. Shibata, Chem. Lett., 375 (1975). in Table 111. K. Toriumi, S. Sato, and Y . Saito, Acta Crystallogr., in press. In each series of dinitro and dicyano complexes, with K. Toriumi, S. Sato, and Y. Saito, paper presented at 34th Annual Meeting of the Chemical Society of Japan, April 2, 1976, Hiratsuka, Japan. (-)ssg-[Co(NO2)2(en)2]+ used as the resolving agent, the M. Shibata, Proc. Jpn. Acad., 50,719 (1974); Nippon Kagaku Zasshi, solubility rule29seems to hold, although it does not always hold 87, 771 (1966). when (-)ssg-[Co(ox)(en)2]+ is used. S. Fujinami and M. Shibata, Bull. Chem. SOC.Jpn., 46, 3443 (1973). In the present work, we obtained the cobalt(II1) complexes Inorg. Synth., 4, 195 (1953). F. P.Dwyer, I. K. Reid, and F. L. Garvan, J . A m . Chem. Soc., 83, 1285 which derive dissymmetries solely from the distribution of (1961). unidentates (unidentate system) and also those complexes F. P. Dwyer, A. M. Sargeson, and I. K. Reid, J. Am. Chem. SOC.,85, which derive dissymmetries from the distribution of bidentates 1215 (1963). H. Yamatera, Bull. Chem. Soc. Jpn., 31, 95 (1958). (bidentate system). It was found that, even if a unidentate S. Nakashima and M. Shibata, Bull. Chem. SOC.Jpn., 48, 3128 (1975). system with a certain chromophore and a bidentate system Y . Ida, K. Kobayashi, and M. Shibata, Chem. Lett., 1229 (1974). with the same chromophores are in the same absolute conC. K. J$rgensen, “Absorption Spectra and Chemical Bonding in Complexes”, Pergamon Press, London, 1962, p 109. figurations, the two systems do not always have the same signs M. Mori, M. Shibata, K. Hirota, K. Masuno, and Y. Suzuki, Nippon in the CD peaks due to the comparable transitions. The Kagaku Zasshi, 79, 1251 (1958). observed CD spectra showed different patterns according to 8. E. Douglas, R. A. Haines, and J. G. Brushmiller, Inorg. Chem., 2, 1194 (1963). the chelate rings of dicarboxylate ions (Cch2-, ox2-, and W. T. Jordan and J. I. Leeg. InorP. Chem.. 13. 955 (1974). mal2-). The situation was the same between a chelate system W. T. Jordan, B. J. Brenn;;, L. RPFroebe, and B. E.’Douglas, Inorg. and the corresponding unidentate system. However, when a Chem., 12, 1827 (1973). A. J. McCaffery, S. F. Mason, and R. E. Ballard, J. Chem. SOC.,2883 bidentate ligand is replaced by the corresponding two uni(1969. - , dentates or a dicarboxylate ion is alternated with another one, A. J McCaffery, S. F. Mason, and B. J. Norman, J. Chem. SOC.,5094 the sign of the peak on the higher frequency side in the Tig (1 965). region never changes for a certain absolute configuration. C. W. Van Saun and B. E. Douglas, Inorg. Chem., 8, 1145 (1969). C. W. Van Saun and B. E. Douglas, Inorg. Chem., 7, 1393 (1968). Registry No. cis,cis-Na[Co(CN)2CO3(NH3)2], 60745-73-5; R. S. Cahn, C. K Ingold, and V. Prelog, Angew. Chem., Int. Ed. Engl., cis,cis-Na[Co(CN)2ox(NH3)2], 60745-74-6; cis,&-K[Co5 -?RS _, _ - (1966) ,___”,. (CN)2mal(NH3)2], 60745-75-7; cis-K[Co(CN)2C03en], 60745-76-8; (29) A. Werner, Ber. Dtsch. Chem. Ges., 45, 1229 (1912). I
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