Organometallics 1995, 14, 5513-55 19
5513
Reactions of [Et3NHl[@-RE)@-CO)Fe2(CO)~] (E = S, Se) Salts with Sulfur(1) Chloride and with Carbon Disulfide. Crystal Structure of the @-PhSe)@-PhCH&C=S)Fe2(CO)6 Complex Li-Cheng Song,* Chao-Guo Yan, and Qing-Mei Hu Department of Chemistry, Nankai University, Tianjin 300071, China
Ru-Ji Wang Department of Chemistry, Tsinghua University, Beijing 100084, China
Thomas C. W. Mak Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong Received June 8, 1995@ The salts of [Et3NHl[(p-RE)gl-CO)Fe2(CO)61(1) react with S2C12 to give double-cluster complexes [(p-RE)Fez(C0)612Cu-S-S-p)(2a-f) (2a, RE = EtS; 2b, PhS; 2c, n-Bus; 2d, t-BUS; 2e, PhSe; 2f, p-CH&sHaSe), whereas the salt of [Et3NHI[Cu-Phse)(p-Co)Fe2(co)61 reacts with CS2 followed by treatment with diverse organic halides to afford single-cluster complexes Cu-PhSe)Cu-ZSC=S)Fe2(CO)s(3a-c) (3a, Z = PhCH2; 3b, PhCOCH2; 3c, EtOzCCHz), doublecluster complexes [@-PhSe)Fe2(CO)6]2(~,~-(LL-S=C-SCH~)~C~&I (3d)and [@-PhSe)Fez(CO)61~[l74-Cu-S=C-SCH2)2CsH41 (3e), and triple-cluster complex [Cu-PhSe)Fez(CO)s13[1,3,5-CuS=C-SCH2)3CsH31 (3f). The crystal structure of 3a was determined by X-ray diffraction techniques.
Introduction Over the past decade, the chemical reactivities of triethylammonium salts of the @-RS)@-Co)Fez(CO)6 anions have been studied e ~ t e n s i v e l y l -relative ~~ to those of their Li+,2Na+,5and Mg+X15salts, as well as Et3N+H salts of the @-RSe)@-CO)Fe2(CO)6anions.6 Reactions of such salts with most electrophiles can be rationalized in terms of their action as iron-centered nucleophiles and may fall into two categories according to the nature of the electrophiles. In one category, reactions with the electrophiles having a leaving group Abstract published in Advance ACS Abstracts, October 15,1995. (1)Seyferth, D.; Womack, G. B.; Dewan, J . C. Organometallics 1985, 4,398. (2)Seyferth, D.; Hoke, J. B.; Dewan, J. C. Organometallics 1987,6, 895. (3)Seyferth, D.; Anderson, L. L.; Davis, W. M. J . Organomet. Chem. 1993,459,271. (4)Seyferth, D.; Ruschke, D. P.; Davis, W. M.; Cowie, M.; Hunter, A. D. Organometallics 1994,13,3834. (5)Seyferth, D.; Womack, G. B.; Archer, C. M.; Dewan, J. C. Organometallics 1989,8,430. (6) Song, L.-C.; Yan, C.-G.; Hu, Q.-M. Acta Chim. Sin. 1995,53,402. (7)Song, L.-C.; Liu, J.-T.; Wang, J.-T. Chem. J . Chin. Uniu. 1989, 10, 905. ( 8 )Song, L.-C.; Wang, R.-J.; Liu, J.-T.; Wang, H.-G.; Wang, J.-T. Acta Chim. Sin. 1990,48, 1141. (9)Song, L.-C.; Liu, J.-T.; Wang, J.-T. Acta Chim. Sin. 1990,48, 110. (10)Song, L.-C.; Li, Y.; Hu, Q.-M.; Liu, R.-G.; Wang, J.-T.Acta Chim. Sin. 1990,48,1180. (11)Song, L.-C.; Wang, R.-J.; Li, Y.; Wang, H.-G.; Wang, J.-T.Acta Chim. Sin. 1990,48, 867. (12)Song, L.-C.; Hu, Q.-M. J . Organomet. Chem. 1991,414,219. (13)Song, L.-C.; Hu, Q.-M.; He, J.-L.; Wang, R.-J.; Wang, H.-G. Heteroatom. Chem. 1992,3,465. (14)Delgado, E.; Hernandez, E.; Rossell, 0.; Seco, M.; Puebla, E. G.; Ruiz, C.J . Organomet. Chem. 1993,455,177. (15)Song, L.-C.; Hu,Q.-M.: Cao. X.-C. Chem. J. Chin. Uniu. 1994, 15, 1331. @
0276-7333/95/2314-5513$09.00/0
gave neutral products in which the organic group replaced the p-CO ligand, such as is shown in ref 5, or the p-CO ligand remains untouched, which was found only in ref 14. In the other category, however, reactions with the electrophiles that have no leaving group initially gave the corresponding salts of other anions and finally gave the neutral products by protonation of the anions from their counterion Et3N+H2or by interaction of the anions with extra electrophiles further added.2 In order to develop the chemistry of such salts, particularly the Se analogs, we initiated the study on the reactions of the Et3N'H salts of @-RE)~-CO)Fe2(CO)6 (E = S, Se) with S2C12 and with CS2. Herein we report the interesting results.
Results and Discussion Reactions of salts [Et3NHl[@-RE)@-CO)Fe2(CO)61 (E = S, Se) (1)prepared from Fe3(C0)12, EtsN, and RSH
or RSeH with S&12 in an approximate molar ratio 2:l resulted in the formation of the S-S-bonded, doublecluster complexes 2. The products 2 could be produced via an intermediate M1 formed by nucleophilic attack of the negatively charged iron in 1 at sulfur atoms in S2C12, followed by the intramolecular displacement of two p-CO groups by the S-S moiety in M1, as shown in Scheme 1. 2a and 2b were previously prepared by another route and identified by comparison of their IR and lH NMR spectra t o those of authentic samples.16J7 (16)Seyferth, D.; Kiwan, A. M.; Sinn, E. J . Organomet. Chem. 1985, 281, 111.
(17)Song, L.-C.; Kadiata, M.; Wang, J.-T. Youji Huaxue 1990,10, 270.
0 1995 American Chemical Society
5514 Organometallics, Vol. 14,No. 12, 1995
Song et al. Scheme 1
S"C1,
2
1
0
*C -2Et3NHC1
R-\yf+o
iyi-"
Fe- Fe (CO)
Fe- Fe ( C O ) (CO), s' -s
4~0) H1
2a
RE
2c-f are new and their constitutions were proven by combustion analysis, IR, 'H NMR spectroscopy, and E1 mass spectrometry. The latter showed the molecular ion M+ for 2f, M+-nCO for 2c and 2d, and the largest fragment (C0)rFezSSePh for 2e. According to the orientations of the S-S and C-E bonds to the subcluster core, FezSE (E = S or Se), there are essentially 10 different conformation isomers in all for double-cluster repulsion interactions between R and subcluster @-RE)@-S)Fe2(C0)6.18319 It is interesting to note that 'H NMR spectroscopy can provide information about the presence of those isomers, which was developed on the basis of the study on the relationship between the structure of (M-C2H5S)2Fe2(CO)620 and King's lH NMR data.21 The lH NMR spectrum of 2a showed one axial ethyl group H ~ppm22and one equatorial ethyl group signal at ~ C 1.92 H ~ppm,22with an integration ratio of signal at ~ C 2.44 3:l;therefore, 2a could not exist as one isomer ii (aeee) or iv (eaea), but should be a mixture of two or more isomers, such as i (aeea) and iii (eeee) or i and vi (eaae) in a ratio of 3:l (Chart 1). Similarly, since the lH NMR spectrum of 2d showed one axial t-Bu signal at d t - ~1.17 u ppm22and one equatorial signal at d t - ~ "1.42 ppm,22and due to the unequal integrations of two t-Bu signals (4: 11, 2d also exists as a mixture, such as i and iii or i and v i with a ratio of 41. The 'H NMR spectrum of 2f only showed one signal forp-CH3 at 6 2.34,which means that the two p-CH3CsH4 are bonded t o E atoms via one type of bond. Thus, 2f may exist as one either i, iii, or vi. Unfortunately, the lH NMR spectra of 2b, 2c, and 2e showed complicated multiplets for their phenyl groups and n-Bu groups attached t o E atoms, which did not provide any useful information for the identification of their isomers. Although the double clusters of type 2 with E = S were prepared previously by oxidative coupling of the monoanion [(LA-RS)(M-S)F~~(CO)& with S02C12,16J7 the double clusters of type 2 with E = Se were first prepared by this new method from the corresponding salts of complexes 1. However, the yields of such double clusters prepared by this method are (18)Shaver, A,; Fitzpatrick, P.; Steliou, K; Butler, I. S. J . Am. Chem. SOC.1979,201, 1313. (19)Seyferth, D.; Henderson, R. S.; Song, L.-C.Organometallics 1982,1, 125. (20) Dahl, L. F.; Wei, C.-H. Inorg. Chem. 1963,2,328. (21) King, R. B. J . A m . Chem. SOC.1962,84,2460. (22) De Beer, J. A.; Haines, R. J. J . Organomet. Chem. 1970,24, 757.
EtS
2b
2c
2d
2e
2f
PhS n-Bus t-Bus PhSe p-CH,C,H,Se
usually low, which is possibly due to the formation of the corresponding byproduct @-RE)J?ez(CO)s. It is known that salts of type 1 with E = S react with CS2 and diverse halides to form dithioformate cluster complexes.2 To compare the reactivity of the salts of type 1 (E = Se) toward CS2 with that of E = S analogs, and to prepare the novel cluster complexes containing both bridged alkylselenido and dithioformate ligands, we carried out the reaction of [Et3NHI[@-PhSe)(M-C0)Fez(CO)sl with CS2, followed by in situ reaction with various organic halides. It was observed that the solution turned cherry red with brisk gas evolution when CS2 was added to the red-brown solution of [Et3NHI[@-PhSe)@-CO)Fez(CO)sl prepared from Fe3(C0)12, PhSeH, and Et3N. This means that the p-CO group was replaced by CS2, and the selenium salt intermediate M2 was formed in which dithioformato acted as a bridging group. Treatment of the intermediate M2 solution with organic mono-, di-, or trihalides followed by further workup gave the corresponding single-cluster complexes 3a-c, double-clustercomplexes 3d-e, and triple-cluster complex 3f, as shown in Scheme 2. The cluster complexes 3a-f are all new and were characterized by combustion analysis and IR, 'H NMR, and mass spectroscopies. Their IR spectra all exhibited two groups of bands: one group consisted of four or five strong peaks in the region of 1960-2100 cm-l and the other had one medium peak around 1000 cm-'. The former was attributed to terminal carbonyls and the latter to the bridged thiocarbonyl C=S group. The C-S vibrational band in free CS2 is situated a t 1533 cm-l, but in CS2 complexes it is usually shifted to the region of 860-1120 cm-1,23As seen from the IR spectra of 3af, the nature of the organic moiety attached to the ex0 sulfur atom may affect the C=S vibrational band. The C=S band in 3a and 3d-f is a t 999 and 1007 cm-l, respectively, while that in 3b and 3c is at 1015 cm-l. This is possible due to the stronger electron-withdrawing effects of the benzoyl and ethoxycarbonyl groups in 3b and 3c than those of the corresponding organic groups in 3a and 3d-f. The 'H NMR spectra of 3a-f indicated the proton signals for their respective organic (23) Patin, H.; Mignani, G.; Mahe, C.; Le Marouille, J.-Y.; Southern, T. G.; Benoit, A.; Grandjean, D. J . Organomet. Chem. 1980,197, 315.
Reactions of [Et3NH][(~-RE)(~-CO)Fez(CO)d
Organometallics, Vol. 14, No. 12, 1995 5515
Chart 1 (CO), (CO),
(CO), (CO),
(CO), (CO),
R
I i,XJ ix: :yrs I \yf-s R
I
R
Fe-
(co)3
Fe-
Fe
-R
Fe
(CO),
R-"\\>(s-s
(CO), (CO),
-R
(CO), (CO),
(ii) a e e e
(i) aeea
ix[
Fe-Fe
(iii) eeee
R
-F e
Fe-'Fe
Fe--'Fe
Fe--Fe
R
1 3
3
iK;" Fe-
I
1
Fe
(viii) aaae
( i x ) aaee
groups, and the mass spectra showed the fragment ions, such as M+ - nCO for 3a-c and smaller fragment ions for 3d-f. With the phenyl groups attached to Se atoms as axial or equatorial groups, there are two possible conformation isomers for 3a-c, three for 3d,e, and four for 3f. Since lH NMR data for the phenyl groups could not provide information for the identification of isomers (due to their complicated multiplets), an X-ray crystal diffraction analysis for 3a was undertaken. The data collection and processing parameters, atomic coordinates, equivalent isotropic thermal parameters, and selected bond lengths and angles are listed in Tables 1-3. Figure 1shows the ORTEP representation of the molecule. As seen from Figure 1,the structure of 3a is very similar to that of p(thioferrocenylmethy1methane thiomethylene-CW2)-1,1,1,2,2,2-hexacarbonylwhere p-methylthiodiiron(abbreviated as Tf hereaRe1-),2~ both contain a butterfly core with Fe2E and FezSC as two wings, with E = Se for 3a and E = S for Tf. The dihedral angle between the two wing planes in 3a is 89.3", which is smaller than the corresponding one in Tf (91').23 The six-coordinate atoms or groups around each iron atom display as a distorted octahedron. The Fe-Fe distance in 3a is 2.648(3) A, which is slightly longer than that of Tf (2.62 A),23but much longer than
those in complexes containing two thioalkyl or thioaryl
bridge^.^^!^^ The angle of S(l)-Se(l)-C(7) = 160.2' reveals that the phenyl group attached to the selenium atom is a t an equatorial position, namely, 3a is an e-type isomer, which can be seen from Figure 1intuitively. The two Fe-Se distances are almost the same [Fe(l)-Se(l) = 2.380(2) A, Fe(2)-Se(l) = 2.368(3) AI. Similar to Tf, the thiocarbonyl C(13)=S(l) in the S(2)-C(13)=S(l) moiety is bridged to Fe(1) via a u bond [Fe(l)-C(13) = 1.98(1)AI with a carbene character23 and to Fe(2) via the donation of an unshared electron pair from S(1)[Fe(2)-S(1) = 2.307(5) AI. In com arison with a typical the bond length of C=S double bond in CS2 (1.554 the double bond C(13)=S(l) extends to 1.63(1) A [corresponding C-S length is 1.658(4)A in Tfl,23but is still much shorter than that of the single bond S(2)-C(13) [1.72(1) A; the corresponding length in Tf is 1.698(4)
K
AI.23
Experimental Section 1. General Comments. All reactions were carried out under an atmosphere of prepurified tank nitrogen. Tetrahy~~
~~
(24)Le Borgne, G.; Grandjean, D.; Mathieu, R.; Poilblance, R. J . Organomet. Chem. 1977,131,429. (25)Henslee, W.;Davis, R. E. Crystallogr. Struct. Commun. 1972, 1, 403. (26)Butler, I. S.;Fenster, A. E. J.Orgunomet. Chem. 1974,66,161.
Song et al.
5516 Organometallics, Vol. 14, No. 12, 1995
Scheme 2
1
..
ph--SeyS7c0
SCH ,COE t
EtOCCH,Br
Fe-
Fe
3c
I
(CO), Fe-se
I>(
(co), Fe
\'d
CH Br
s CH Br
S
Fe-Fe
S
!=weI
Fe- F e
Ph
t
S
s\
C\=WPh Fe- F e
Fe- Fe
drofuran (THF) was distilled under nitrogen from sodium/ benzophenone ketyl, triethylamine from potassium hydroxide, sulfur(1) chloride from elemental sulfur, and carbon disulfide from phosphorus pentoxide. Ethyl, n-propyl, n-butyl, and tertbutyl mercaptans, thiophenol, benzyl bromide, ethyl bromoacetate, and bromoacetophenonewere of commercial origin and used without further purification. 1,3-Bis(bromomethyl)benzene, 1,4-bis(bromomethyl)benzene,1,3,5-tris(bromomethy l l b e n ~ e n e triiron ,~~ dodecacarbonyl,28and b e n z e n e s e l e n ~ l ~ ~ were prepared by literature procedures. The progress of all reactions was monitored by thin-layer chromatography (TLC). Products were purified by column (27) Werner, W. J . Org. Chem. 1962, 17, 523. (28) King, R. B. Organometallic Syntheses; Academic Press: New York, 1965; Vol. 1, Transition-Metal Compounds, p 95. (29)Foster, D. G. Organic Syntheses; Wiley: New York, 1955; Collect. Vol. 111, p 771.
chromatograF.-y (30 x 2.4 cm, 200-300 mesh silica gt-, and by TLC (20 x 25 x 0.025 cm, silica gel G).Chromatography was completed without the exclusion of atmospheric oxygen or moisture. The eluents were light petroleum ether (60-90 "C) and methylene chloride, which were chemical reagents and used without further purification. Solid products were recrystallized from deoxygenated, mixed solvents of CHzCldpetroleum ether. Melting points were determined on a Yanaco MP-500 melting point apparatus and were uncorrected. Combustion analysis was performed on a 240C Model analyzer. Proton NMR spectra were recorded on a JEOL FX-9OQ spectrometer with a CDC4 solvent and a TMS internal standard. Infrared spectra were obtained on a NICOLET FT-IR 5DX spectrophotometer with a KBr disk. Mass spectra were obtained with a HP 5988A spectrometer. 2. Reaction of [EtsNHI[(I(-RE)(I(-CO)Fe2(CO)el (1) with
Reactions of [Et~Hl[(~-RE)(~-CO)Fe2(CO)d
Organometallics, Vol. 14, No. 12, 1995 5517
Table 1. Data Collection and Processing Parameters for 3a molecular formula molecular weight color and habit crystal size (mm3) crystal system space group unit cell parameters
density (calcd, g ~ m - ~ ) Rigaku R-AXIS I1 camera length (mm) frame number exposure time (min) radiation absorption coefficient (mm-') collection range unique data measured Rint (from merging of equiv reflections) obs data with lFol z 10u(lFoI),n no. of variables, p weighting scheme RF = ZllFol - l~cllEl~ol R w = [ X : ~ ( l F o i- I F c 1 ) 2 E ~ I ~ 0 1 2 1 1 ' 2 s = [XwWol - IFcl)2/(n -p)11'2 largest and mean A h residual extrema in final difference map ( e k 3 )
Table 2. Atomic Coordinates ( x 104) and Equivalent Isotropic Tem erature Factorsa ( x lo4 & for Se and Fe; x103 for Others) for 3a
%
atom
X
2957(2) 1354(2) 3884(2) 4292(4) 1956(4) 764(12) - 1016(11) -294( 11) 4056(12) 6756(11) 2746(12) 987(14) -85(15) 362(13) 3998(15) 5669(15) 3183(14) 2407(14) 3323(15) 3013(16) 1814(17) 917(17) 1225(16) 2621(13) 3464(14) 3030(13) 2761(15) 2334(17) 2326(15) 2599(16) 2981(16) a
Y
339(1) -412(1) -205(1) -922(2) -1463(2) -1453(4) -514(5) 483(5) -1173(5) 326) 597(5) -1028(7) -466(6) 128(7) -800(7) 98(7) 299(6) 1141(6) 1529(6) 2133(7) 2387(7) 2029(6) 1418(6) -969(5) -1882(7) -2269(6) -2877(7) -3250(7) -2981(7) -2380(7) -2025(8)
CzoHlzFezO6SzSe 603.08 red plate 0.05 x 0.10 x 0.10 monoclinic P21h (No. 14) a = 9.584(2)A b = 21.871(4) A c = 11.061(2)A /3 = 98.92(3)" 2=4 V = 2291(1) A3 F(000) = 1192 1.749 imaging plate size, 200 x 200 mm 69.95 (start angle -20.0') 24 (oscillation angle 6") 16 graphite-monochromatized Mo Ka,?, = 0.710 73 A 3.071 o 5 h I12, o c 12 5 25, -13 5 i 5 13; ze = 55" 4101 0.074 1746 256 w = l/u2 (37 0.066 0.066 2.91 0.24 and 0.04 +0.92 to -0.44
Table 3. Selected Bond Lengths (A) and Bond Angles (deg) for 3a atom
z
3626(2) 2675(2) 2078(2) 3623(4) 4721(4) 993(10) 4069(11) 1071(10) 289(12) 2381(12) 67(11) 1653(13) 3582(15) 1679(13) 1021(15) 2290(16) 889(13) 3131(13) 2572(15) 2389(16) 2703(16) 3229(14) 3416(15) 3744(12) 5517(13) 6483(13) 6346(15) 7246(15) 8356(16) 8574(16) 7628(16)
U , is defined as one-third of the trace of the orthogonalized
U tensor. Sulfur(1)Chloride. A 100 mL three-necked round-bottomed flask equipped with a stir-bar, a N2 inlet tube, and serum caps was charged with 1.50 g (2.98 mmol) of Fe3(C0)12 and 40 mL of THF. To the resulting green solution were added 0.50 mL (3.58 mmol) of triethylamine and about 3 mmol of the corresponding mercaptan, thiophenol, or areneselenol. The solution immediately turned red-brown and was stirred for 10 min in
atom
distance 2.648(3) 1.76(2) 1.79(1) 2.368(3) 1.18(2) 1.12(2) 1.63(1) 1.82(1) angle 55.9(1) 94.0(5) 160.8(5) 93.5(4) 82.3(4) 56.3(1) 75.9(1) 101.1(5) 100.1(5) 94.7(5) 167.5(5) 177(1) 112.4(4) 121(1) 106.1(7) 120.7(7)
atom Fe(1)-Se( 1) Fe(l)-C(2) Fe(l)-C(13) Fe(2)-S(l) 0(3)-C(3) Se(l)-C(7) S(2)-C(13) C(14)-C(15) atom
distance
angle 149.8(5) 107.0(5) 102.1(7) 98.8(5) 75.7(4) 81.1(1)
156.7(5) 88.2(5) 155.6(6) 92.0(5) 178(1) 67" 112.1(5) 92.7(5) 115.6(7) 123.8(8)
llO(1)
the case of areneselenol and for 30 min in the case of mercaptan and thiophenol. The resulting [EtsNH][@-RE)@CO)Fe2(C0)6] reagent (1) then was utilized in situ without further purification. 2.1. Preparationof 2a. The THF solution of 1 (RE = EtS) prepared by using EtSH as above was cooled to -78 "C with a dry ice/acetone bath, to which was added 0.13 mL (1.6 mmol) of sulfur(1) chloride. The reaction mixture was maintained for 10 min at -78 "C and then allowed to warm to room temperature and stirred for an additional 2 h. TLC analysis of the reaction mixture indicated the formation of two major orange-red products. The solvent was removed in uacuo to give a dark red residue, which was purified by column
5518 Organometallics, Vol. 14, No. 12, 1995 0151
v
OI4'
Figure 1. ORTEP view of 3a as drawn with 35% probability ellipsoids. chromatography. Elution with 1:9 (vlv) CHzClz/petroleum ether gave a red oil, which was further purified by TLC. Elution with 1:18 (vlv) CHzClz/petroleum ether gave two red bands. The first red band gave 0.076 g (4%) of @-EtS)zFez(CO)6,which was identified by comparison of its melting point and lH NMR spectrum with those given in the l i t e r a t ~ r eThe .~ second major red band gave 0.331 g (30%)of [@EtS)Fez(C0)6]2@-S-S;u) (2a)as a slightly air-sensitive red crystal, which was also identified by comparison of its melting point and 'H NMR spectrum with those of an authentic ~ a m p 1 e . I ~ 2.2. Preparation of 2b. The same procedure as in section 2.1 was followed, but 1 where RE = EtS was replaced by 1 where RE = PhS and gave two major products. The first orange band gave 0.349 g (24%) of @-PhS)zFe~(cO)6, which was identified by comparison of its melting point and lH NMR spectrum with those given in the l i t e r a t ~ r e The . ~ ~ second red band gave 0.080 g (6%)of [(~-PhS)Fez(CO)6]z@-s-s-~) (2b)as a slightly air-sensitive red solid, which was also identified by comparison of its melting point and lH NMR spectrum with those of an authentic sample.16 2.3. Preparation of 2c. The same procedure as in section 2.1 was followed, but 1 where RE = EtS was replaced by 1 where RE = n-BUS and gave two major products. The first red band gave 0.054 g (4%)of (~m-BuS)zFez(CO)6, which was identified by comparison of its lH NMR spectrum with that given in the literature.22 The second major red band gave 0.294 g (30%) of [(-n-BuS)Fez(C0)6]2@-s-s-/*) (2c) as a slightly air-sensitive red solid (mp 85-86 "C). Anal. Calcd for CzoH18Fe4012S4: C, 29.95; H, 2.26. Found: C, 29.90; H, 1.98. IR (KBr disk): terminal CEO 2065(vs), 2049(vs), 1991(vs) cm-l. IH NMR (CDC13): 6 0.60-2.70 (m, 18H, 2CHzCHzCHzCH3). MS (EI) mlz (relative intensity): 718 [(M - 3CO)+, 0.61, 662 [(M - 5CO)+,0.41, 578 [(M - 8CO)+,0.61, 550 [(M 9CO)+, 0.51, 522 [(M - loco)+, 3.01, 494 [(M - 11CO)+,8.21, 466 [(M - 12CO)+, 1.81, 402 [(CO)6FezSH.SBu-n+,2.61, 374 [(CO)sFezSH*SBu-n+,5.21,346 [(CO)4FezSH.SBu-n+,8.11,318 [(C0)3FezSH.SBu-n+,19.71, 233 (FezS*SBu-n+,K O ) , 201 (FezSBu-n+, 4.01, 176 (Fez&+, 24.31, 144 ( F e z S , 11-41,112 (Fez+, 4.81, 90 (n-BUSH', 6.11, 57 (n-Bu+, 21.61, 56 (Fe+, loo), 41 (CHz=CKCHz+, 85.6). 2.4. Preparation of 2d. The same procedure as in section 2.1 was followed, but 1 where RE = EtS was replaced by 1 where RE = t-BUS and gave two major products. The first red band gave 0.058 g (4%) of (pu-t-BuS)zFez(C0)6, which was identified by comparison of its melting point and lH NMR spectrum with those given in the literature.22 The second major red band gave 0.616 g (52%) of [(~-t-BuS)Fez(Co)6]2@S-S-p) (2d) as a slightly air-sensitive red crystal (mp 140 "C (dec)). Anal. Calcd for CzoHlsFe401~S4:C, 29.95; H, 2.26. Found: C, 29.77; H, 2.23. IR (KBr, disk): terminal C=O 2065(s), 2032(vs), 2008(s), 1983(vs) cm-'. 'H NMR (CDC13): 6 1.17 [ s , a-C(CH&], 1.42 [s, e-C(CH&], d e = 4:l. MS (EI) mlz (relative intensity): 522 [(M - loco)+,0.71, 494 [(M (30)Nametkin, N. S.; Tyurin, V. D.; Kukina, M. A. J. Organomet. Chem. 1978,149, 355.
Song et al. 11CO)+, 1.81, 466 [(M - 12CO)+,0.51, 409 (Fe&Bu-t+, 0.71, 352 (Fe4S4+,2.0), 233 (FezS.SBu-t+, 2.61, 177 (Fe2S.SHf, 7.11, 176 (Fez&+, 1.11,144 (FezS+,0.6),112(Fez+,1.2),90 &BUSH+, 16.8), 89 (&BUS+,0.61, 57 (t-Bu+, 37.31, 56 (Fe+, 33.71, 41 (CHz=CHCHz+, 100). 2.5. Preparation of 2e. The same procedure as in section 2.1 was followed, but 1 where RE = EtS was replaced by 1 where RE = PhSe and gave two major products. The first red band gave 0.337 g (19%) of @-PhSe)zFez(CO)e,which was identified by comparison of its melting point and 'H NMR spectrum with those of an authentic sample.6 The second red band gave 0.122 g (9%) of I(/*-PhSe)Fez(CO)6lz(-S-S-/*)(2e) as a slightly air-sensitive red solid (mp 190 "C (dec)). Anal. Calcd for C24HloFe4012SzSez: C, 30.80; H, 1.08. Found: C, 30.75; H, 0.98. IR (KBr, disk): terminal CEO 2082(s), 2057(vs), 2032(vs), 1991(vs), 1975(vs) cm-l. lH NMR (CDC13): 6 7.16-6.80 (m, 10H, 2CsH5). MS (EI, soSe) mlz (relative intensity): 413 [(C0)4Fe&SePh+, 98.61, 357 KC0)zFezS.SePh+, 12.41, 301 (FezS.SePh+, 5.61, 269 (FezSePh+,3.71, 224 (FezS.Se+, 8.6), 196 (FezSe+,4.71, 144 (FezS, 4.81, 112 (Fez+, 8.21, 77 (C6H5+,8.61, 56 (Fe+, 26.8). 2.6. Preparation of 2f. The same procedure as in section 2.1 was followed, but 1 where RE = EtS was replaced by 1 where RE = 4-C&C6H4Se and gave two major products. The first red band gave 0.439 g (24%)of @-4-CH3CsH4Se)zFez(c0)6 as an air-stable red solid. It is a new compound (mp 96-98 "C). Anal. Calcd for CzoH14Fez06Sez: C, 38.75; H, 2.28. Found: C, 38.83; H, 2.22. IR (KBr disk): terminal CEO 2032(s), 2000(vs), 1967(vs)cm-'. 'H NMR (CDC13): 6 2.20 (s, 6H, 2CH3), 6.88,6.96, 7.08, 7.18 (AA'BB' quartet, 8H, 2CsH4). MS (EI, aoSe)mlz (relative intensity): 622 (M+, 0.9), 566 [(M - 2 c o ) + , ~ 2 1 , 5 3 8[(M - 3 c o ) + , 0.61,510 [(M - 4 c o ) + , 0.41, 482 [(M - 5CO)+, 1.41, 454 [(M - 6CO)+, 8.21, 363 (FezSeSeC&CH3-4+, 1.21, 272 (FezSez+,21.71, 283 (FezSeCsH4CH3-4+, 1.5), 269 (FezSeC6&+, 7.11, 192 (FezSe+, 9.41, 182 (CH3C&C6H4CH3+, 26.7),167 (C~H~SI?',18.4), 112 (Fez+,3.81, 91 (C&CH3+, loo), 56 (Fe+,16.5). The second red band gave 0.095 g (7%)of [(~-4-CH3CsH4Se)Fez(co)61~(~-s-S-/*) (20 as a slightly air-sensitive red solid (mp 105 "C (dec)). Anal. Calcd for C Z ~ H I ~ F ~ ~ O & C, S32.40; ~ ~ : H, 1.46. Found: C, 32.19; H, 1.43. IR (KBr disk): terminal CEO 2082(s), 2057(vs), 2032(vs), 1991(vs) cm-'. 'H NMR (CDC13): 6 2.34 (s, 6H, 2CH3), 7.09, 7.18, 7.33, 7.44 (AA'BB' quartet, 8H, 2C6H4). MS (EI, 80Se)mlz (relative intensity): 315 (FezS.SeC6H&H3-4+, 1.3),282(FezSeC&CH3-4+, 1.4),224(FezS.Se+,351,192 (FezSe+,2.1),171(4-CH&&Se+, 23.2),144 (FezS, 3.2),112 (Fez+, 1.91, 91 (C6&CHz+, loo), 56 (Fe+, 11.7). 3. Reactions of [EtsNHl[Cu-PhSe)Cu-CO)Fez(CO)sl with Carbon Disulfide. Standard in Situ Preparation of [EtsNHl[(I(-PhSe)Ol-SC=S)Fez(CO)sl (M2). A 100 mL threenecked flask equipped with a magnetic stir-bar, a Nz inlet, and serum caps was charged with 1.50 g (2.98 mmol) of Fe3(C0)12 and 40 mL of THF. To the resulting green solution were added 0.50 mL (3.58 mmol) of triethylamine and 0.32 mL (3.03 mmol) of benzeneselenol, which was stirred for 10 min. When 0.60 mL (10.0 mmol) of CS? was added to this THF solution of [Et3NHl@-PhSe)(/*-CO)Fez(CO)61, gas evolution was observed and the color of solution changed from red-brown to cherry red in 30 min. The [E~~NH]~~-P~S~)OL-S=~-S-)F~Z(C~)~] (M2)solution was thus prepared and utilized in situ without further purification. 3.1. Preparation of 3a. To the solution prepared as above was added 0.72 mL (6.0 mmol) of benzyl bromide. The reaction mixture was stirred for 2 h at room temperature. TLC analysis indicated that two main red products were formed. The solvent was removed in uucuo to give a red residue, which was subjected to column chromatography. Elution with 1:9 (vlv) CHzCldpetroleum ether followed by evaporation of the solvent gave 0.322 g (18%)of @-PhSe)zFez(CO)6,which was identified by comparison of its melting point and lH NMR spectrum with those of a n authentic sample,6 and 1.016 g (3a) as a red air(57%) of @-PhSe)(/*-PhCHzSCS)Fez(C0)6
Reactions of [Et3NHl[(~-RE)(~-CO)FegCO)~
Organometallics, Vol. 14, No. 12, 1995 5519
stable solid (mp 116-117 "C). Anal. Calcd for C20HlzFez06Sz3.5. Preparation of 3e. A procedure similar to that in Se: C, 39.83; H, 2.01. Found: C, 39.79; H, 2.03. IR (KBr section 3.1 was followed, but 0.370 g (1.4 mmol) of 1,Cbis(bromomethy1)benzene was used instead of benzyl bromide. disk): terminal C=O 2065(s), 2016(vs), 1983(s), 1867(s) cm-', Elution with 1:9 (v/v) CH2Clz/petroleum ether yielded 0.303 g C=S 999(m) cm-l. lH NMR (CDC13): 6 4.35 (s, 2H, CHz), 7.08-7.64 (m, 10H, 2C6H5). MS (EI, 8oSe) mlz (relative (17%)of (p-PhSe)2Fez(CO)eand then gave 0.503 g (30%)of [(pintensity): 520 [(M - 3CO)+, 1.01, 492 [(M - 4CO)+, 0.71, 436 PhSe)Fe2(C0)~]~[1,4-(p-~cscH2)2c6H4] (3e)as a red air-stable [(M - 6CO)+,3.31, 345 (Fe2SePhCSzc, 1.91, 301 (FezS.SePh+, solid (mp 52-54 "C). Anal. Calcd for C ~ ~ H I S F ~ ~ OC,I ~ S ~ S ~ ~ : 4.0),269 (FezSePh+,6.1),224(Fe&Se+, 6.0),192 (FezSe+,3.71, 36.20; H, 1.61. Found: C, 36.26; H, 1.54. IR (KBr disk): 157 (PhSe+, 11.71, 144 (Fe2S+, 2.31, 91 (C&CH2+, loo), 77 terminal C=O 2065(s), 2024(vs), 2000(s), 1983(s) cm-l, C=S 1007(m) cm-l. 'H NMR (CDC13): 6 4.16,4.41 (s, s, 4H, 2CH2), (C6H5+, 15.61, 56 (Fe+, 2.9). 7.12-7.60 (m, 14H, 2C6H5, C6H4). MS (EI, 80Se)mlz (relative 3.2. Preparation of 3b. A procedure similar to that in intensity): 269 (FezSePh+, 0.3), 192 (FezSe+,0.21, 157 (PhSe+, section 3.1 was followed, but 0.995 g (5.0 mmol) of bromo36.91, 105 (C&C6H&H2+, 21.8), 104 (CH2CsH&H2+, loo), 78 acetophenone was used instead of benzyl bromide. Elution with 1:18 (v/v) CHzClz/petroleum ether yielded 0.310 g (18%) (CsHs', 26.3), 77 (C6H5+,36.8). 3.6. Preparation of 3f. A procedure similar to that in of (pu-PhSe)2Fe2(CO)6.Further elution with 3:7 (vlv) CH2Cld section 3.1 was followed, but 0.358 g (1.0 mmol) of 1,3,5-trispetroleum ether afforded 0.906 g (48%)of (p-PhSe)b-PhCOCHzSCS)Fe2(CO)6(3b) as a red air-sensitive solid (mp 38-40 "c). (bromomethy1)benzene was used instead of benzyl bromide. Elution with 1:18 (vlv) CHzClz/petroleum ether gave 0.334 g Anal. Calcd for C21H12Fe207S2Se: C, 39.97; H, 1.92. Found: (19%)of b-PhSe)zFe2(CO)6. Further elution with 1:5 (v/v)CH2C, 40.36; H, 1.78. IR (KBr disk): terminal C=O 2065(s), Clz/petroleum ether yielded 0.259 g (16%) of [b-PhSe)Fez2024(vs), 2000(s), 1983(s) cm-l, C=O 1680(m) cm-', C=S 1015(m) cm-l. 'H NMR (CDC13): 6 4.74 (s, 2H, CH2), 7.34(C0)6]3[1,3,5-(p-SCScH2)3c6H3] (30 as a red air-stable solid (mp 78-80 "c). Anal. Calcd for C48Hz4Fe60i8SsSe3: c, 34.88; 8.20 (m, 10H, 2C6H5). MS (EI, 80Se)mlz (relative intensity): H, 1.46. Found: C, 34.76; H, 1.39. IR (KBr disk): terminal 548 [(M - 3CO)', 0.4],520 [(M - 4CO)+,0.41,464 [(M - 6CO)+, 2.1],301 (Fe&SePh+, 1.7),269 (FezSePh+, 4.2),224 (FezSSe+, CEO 2065(s), 2032(vs), 2000(s), 1983(s) cm-l, C=S 1007(m) cm-l. 'H NMR (CDC13): 6 3.94-4.12, 4.16-4.48 (m, m, 6H, 4.11, 192 (FezSe+,5.21, 157 (PhSe+,24.71, 144 (FezS+,3.51, 119 3CH2), 7.04-7.60 (m, 18H, C6H3, 3CsH5). MS (EI, 8oSe)m/z (PhCOCH2+,1.91, 105 (PhCO+,69.9), 91 (CsH&H2+, 22.81, 77 (relative intensity): 346 (FezSePh.SCSH+,0.3), 314 (Fe2SePh.(C6H5+, 1001, 56 (Fe+, 9.5). SCH+, 37.51, 301 (FezSePhS+, 0.41, 269 (FezSePh+, 0.71, 224 3.3. Preparation of 3c. A procedure similar t o that in (FezSeW, 1.3),192 (FezSe+,031,157 (PhSe+,91.4),144(Fe2S+, section 3.1 was followed, but 0.56 mL (5.0 mmol) of ethyl bromoacetate was used instead of benzyl bromide. Elution 0.91, 117 [Cs&(C&)3+, 15.71, 104 (CHzCsH4CH2+, 1.81, 91 with 1:18 (v/v) CHzCLJpetroleum ether yielded 0.392 g (22%) (CsH&H2+, 19.41, 78 (C6H6+, 16.41, 77 (C6H5+,loo), 56 (Fe+, of (pPhSe)&'ez(CO)6. Further elution with 1:4 (vlv) CH2Clz/ 2.3). 4. Crystal Structure Determination of 3a. Details of petroleum ether afforded 0.836 g (47%) of (p-PhSe)(p-EtOzcrystal parameters, data collection, and structure refinement CCH2SCS)Fe2(CO)6(3c) as a red air-stable solid (mp 74-75 are given in Table 1. Raw intensities were collected on a "C). Anal. Calcd for C17H&e2O&Se: C, 34.09; H, 2.02. Rigaku R-AXIS I1 camera with a rotating anode source (50 Found: C, 34.19; H, 2.13. IR (KBr disk): terminal C e O kV, 150 mA) at room temperature (294 K). Patterson super2065(s), 2032(vs), 2008(s), 1983(s), 1951(s) cm-', C=O 1721 position yielded the positions of all non-hydrogen atoms, which cm-l, C=S 1015(m) cm-l. lH NMR (CDC13): 6 1.20 (t, J = were subjected to anisotropic refinement. All hydrogens were 7.2 Hz, 3H, CH3), 3.91 (s, 2H, CH2CO), 4.16 (9, J = 7.2 Hz, 2H, CH2), 7.04-7.80 (m, 5H, C6H5). MS (EI, 80Se)mlz (relative generated geometrically (C-H bonds fixed at 0.96 A) and allowed to ride on their respective parent C atoms; they were intensity): 544 [(M - 2CO)+,2.01, 516 [(M - 3CO)+,21.71,488 assigned the same isotropic temperature factors (U= 0.08 A2) [(M - 4CO)+,14.41, 460 [(M - 5CO)+, 0.91, 432 [(M 6CO)+, and included in the structure factor calculations. Computa58.3],387 (Fe2SePh.SCSCH2COf, 531,359 (FezSePh*SCSCH2+, tions were performed using the SHELXTL PC program pack2.8), 346 (FezSePh*SCSH+,1001, 345 (FezSePh*SCS+,13.91, age on a PC 486 computer. Analytical expressions of atomic 301 (FezSePh.S+, 18.5),269 (FezSePh+,331, 192 (FezSe+,61.71, scattering factors were employed, and anomalous dispersion 157 (PhSe+,52.71, 144 (Fe2S+,28.21, 112 (Fez+,14.7),77(C6H5+, corrections were i n ~ o r p o r a t e d . ~ ~ 62.1), 56 (Fe+,42.1). 3.4. Preparation of 3d. A procedure similar to that in Acknowledgment. We are grateful t o the National section 3.1 was followed, but 0.370 g (1.4 mmol) of 1,3-bis(bromomethy1)benzene was used instead of benzyl bromide. Natural Science Foundation of China and the State Key Elution with 1:18 (v/v) CH&lz/petroleum ether yielded 0.403 Laboratory of Elemento-OrganicChemistry for financial g (23%) of (p-PhSe)2Fe2(CO)6. Further elution with 1:4 (vlv) support of this work. CH&lz/petroleum ether afforded 0.501 g (30%) of [(p-PhSe)F~z(C~)~]~[~,~-OL-SCSCH~)~C~H~] (3d)as a red air-stable solid Supporting Information Available: Tables of crystalZ S ~ S ~ ~lographic : (mp 44-46 "C). Anal. Calcd for C ~ ~ H I ~ F ~ ~ OC,I 36.20; data, positional and thermal parameters including H, 1.61. Found: C, 36.58; H, 2.01. IR (KBr disk): terminal hydrogen atoms, and anisotropic parameters (6 pages). OrderCEO 2065(s), 2024(s), 2000(s), 1983(s) cm-', C=S 1007(m) ing information is given on any current masthead page. cm-'. 'H NMR (CDC13): 6 3.96-4.20, 4.24-4.48 (m, m, 4H, OM950432W 2CHz), 7.12-7.72 (m, 14H, 2C6H5, C6H4). MS (EI, 80Se)mlz (relative intensity): 157 (PhSe+, 94.81, 105 (CH3C6H&H2+, (31)International Tables for X-ray Crystallography; Kynoch Press: 16.71, 104 (CHzC6H4CHz+, 97.51, 91 (CsH&H2', 29.31, 78 Birmingham, 1974 (now distributed by Kluwer: Dordrecht, The Netherlands); Vol. 4, pp 55, 99, 149. (C6H6+,84.61, 77 (CsH5+, 100).
