Organometallics 1995, 14, 1023-1029
1023
Chemistry of [(q6-C6HsOH)Mn(CO)3]BF4: Synthesis of Disubstituted Cyclohexadienylmanganese Complexes from (C6H&)Mn(C0)2L (L = c o , PPh3, P(OMe)3) Si-Geun Lee, Jeong-A Kim, Young Keun Chung,"Tae-Sung Yoon, Nam-jun Kim, and Whanchul Shin*Ja Department of Chemistry, College of Natural Sciences, Seoul National University, Seoul 151- 742,Korea
Jaecheon Kim and Kimoon Kimlb Department of Chemistry and Center for Biofunctional Molecules, Pohang Institute of Science and Technology, P.O. Box 125, Pohang, Kyung-Buk 790-600, Korea Received September 6, 1994@ Treatment of [(q6-phenol)Mn(C0)31+(1+)with t-BuOK led to [(q5-C6H50)Mn(C0)3][2(CO)l. Treatment of 1+ with NMO or T W O ( 1 equiv) and PR3 (3 equiv) led to the oxocyclohexadienyl complex [(q5-C6H5O)Mn(CO)zPR31[2(PR3) (R = Ph, OMe)]. 2(L) reacts consecutively with a nucleophile (Nu) and a n electrophile (E) to give reasonable to high yields of double(3)(L = CO, PPh3, P(OMe)3). Demetaaddition products, [{6-Nu-q5-1-EO-C~H5}Mn(CO)~Ll lation of 3 by using Jones reagent resulted in a high yield of ortho-disubstituted arenes. X-ray crystallographic studies of 2(CO), 2(PPh3), and 3 (L = P(OMe)3, Nu = Ph, E = C(0)CH3) have been determined.
Introduction In 1976, the first oxocyclohexadienyl complex Rh(H)(Cd+,O)(PPh&was reported by Wilkinson.2 Since then, many related organometallic compounds have been d e ~ c r i b e d . ~ However, -~ little of their chemistry has been reported. The acidity of phenol is considerably enhanced on complexation to a transition metal. Thus, most of the oxocyclohexadienyl complexes have been synthesized by deprotonation of the phenol complex. A manganese oxocyclohexadienyl compound prepared by the deprotonation of a phenol complex was reported by Pauson: who made the phenol complex via the hydrolysis of [(CsH5F)Mn(C0)31+. In a continuation of our study of (arene)Mn(C0)3+ cations, we recently found that the manganese phenol complex was obtained in high yield from the reaction of phenol with Mn(C0)EBFd in methylene chloride solution. Herein, we report the synthesis and reactivity of (~5-oxocyclohexadienyl)manganese complexes. The chemistry described here, summarized in Scheme 1, originates with the hydroxide [(C6H&H)Mn(C0)31+( 1 9
Experimental Section All reactions were conducted under nitrogen using standard Schlenk-type flasks. Workup procedures were done in air. Elemental analyses were done at the Korea Basic Science Center. lH and 13CN M R spectra were obtained with a Varian Abstract published in Advance ACS Abstracts, January 15, 1995. (1) (a) X-ray analyses for 2(CO) and 2(PPh3);(b) X-ray analysis for 3 (L = P(OMe)3,Nu = Ph, E = C(0)CHs). (2) Cole-Hamiloton,D. J.; Young, R. J.; Wilkinson, G. J . Chem. SOC., Dalton Trans. 1976,1995. ( 3 )White, C.; Thompson, S. J.; Maitlis, P. M. J. Organomet. Chem. 1977,127,415. (4)Fairhurst, G.; White, C. J . Organomet. Chem. 1978,160,C17. ( 5 ) Chaudret, B.; He, X.; Huang, Y. J . Chem. SOC., Chem. Commun. 1989,1844. Loren, S.D.;Campion, B. K.; Heyn, R. H.; Tilley, T. D.; Bursten, B. E.; Luth, K. W. J . Am. Chem. SOC.1989,111,4712. (6)Trahanovsky, W. S.;Hall,R.A. J . Am. Chem.Soc. 1977,99,4850. (7) Bhasin, K.K.; Balkeen, W.; Pauson, P. L. J . Organomet. Chem. 1981,201,C25. ( 8 ) Aldrich Chemical Co., NMR 2 (1) 853D. @
XL-200 instrument. Infrared spectra were recorded on a Schimadzu IR-470 spectrophotometer (spectra measured as films on NaCl by evaporation of solvent). Mass spectra were recorded with a VG ZAB-E double-focusingmass spectrometer. Synthesis of l+.7A stirred solution of Mn(C0)sBr (3.0 g, 11 mmol) in 200 mL of CH2Clz was treated with AgBF4 (1.1 equiv) for 5 h at room temperature with exclusion of light. Phenol (1.6g, excess) was added to the solution of Mn(CO)sBF4 in CHZClz. The reaction mixture was refluxed for 24 h. The product was isolated by evaporation of the solvent, followed by recrystallization with acetoneldiethyl ether. The yield of [(CsH50H)Mn(C0)31BF4was 93%. When Mn(C0)&104 was used instead of Mn(C0)5BF4, the yield of was 75%. IR: YCO 2073, 2008 cm-'. Anal. Calcd for C&&1Mn07 [(C,&OH)Mn(C0)3lC104): C, 32.51; H, 1.82. Found: C, 32.40; H, 1.95. Synthesis of 2. (1) Synthesis of 2(CO). t-BuOK (6.0 mmol) in 20 mL of THF was added dropwise to a solution of [(CsH50H)Mn(C0)31BF4(1.59 g, 6.0 mmol) in 30 mL of THF at room temperature. After stirring for 1 h, diethyl ether (50 mL) was added to the solution. The solution was filtered through Celite and evaporated. Purification by column chromatography (silica gel, ethyl acetate) gave 1.30 g (93%). IR: YCO 2040, 1960 cm-l; VC=O 1618 cm-l. 13C NMR (CDCl3): 6 218.7 (C=O), 166.62 (C=O), 105.06, 84.29, 76.36 ppm. (2) Synthesis of 2(PRs) (R = Ph, OMe). 4-Methylmorpholine N-oxide (NMO)was used for the synthesis of 2(P(OMe)3) and trimethylamine N-oxide ( T W O ) for the synthesis of 2(PPh3). [(C6H50H)Mn(C0)31BF4 (1.19 g, 4.5 mmol) was stirred into 50 mL of CHzCl2 at room temperature while NMO (0.58 g, 5.0 mmol) in 5 mL of CHzClz was added dropwise. After 1 h, P(OMe)3 (1.6 mL, 13.5 mmol) was added t o the red solution. After being stirred for 3 d, the resulting yellow solution was quenched with water and extracted with diethyl ether. The organic layer was separated, dried over anhydrous MgS04, and evaporated to yield yellow residues. Purification by column chromatography (silica gel, acetone) gave 1.26 g (85%)of the product 2(P(OMe)3). Mp: 127 "C. IR: vco 1974, 1913 cm-l, YC-0 1555 cm-l. lH NMR (acetone&& 6 5.785.70 (br t, 2 H, H2s4),5.01-4.92 (br t, 1 H, H3), 4.84-4.70 (br d, 2 H, H1z5),3.67 (d, 11.47 Hz, 9 H, P(OMe)3)ppm. 13CNMR (acetone&& 6 225.4 (CEO), 159.01(C=O), 130.1,119.6,116.3, 53.0 ppm. HRMS: mlz (M+) calcd 327.9908, obsd 327.9913.
0276-733319512314-1023$09.00/0 0 1995 American Chemical Society
Lee et al.
1024 Organometallics, Vol. 14, No. 2, 1995 Scheme 1
9 E = CH3 ,C,H5 ,C3H5
I+ 2) \E
WMnO E (W2L
a E = CH3C0, C2H5C0, SiMe,t-Bu
In the same way as above, 2(PPh3) was obtained in 73% yield. Mp: 73 "C. IR: YCO 1960,1901,YC-o 1580 cm-'. 'H NMR (acetone-&): 6 7.7-7.3 (m, 15 H, Ph), 6.15-5.85(br, 3 H, H233*4), 5.2-5.0 (br, 2 H, H1*5)ppm. 13C NMR (CDC13): 6 226.4 (CEO), 157.51(C=O), 134.8,132.7,130.4,129.2,128.6, C,~66.96; P: 118.9,115.7 ppm. Anal. Calcd for C Z ~ H Z O M ~ O H, 4.32. Found: C, 66.4;H, 4.31. Synthesisof 3. (1)Typical procedure when the electrophile was an alkyl halide: MeLi (0.5 mmol) was added to the solution of 2(PPh3) (0.1g, 0.21mmol) in 10 mL of dimethoxyethane a t 0 "C. After stirring for 15 min, the reaction mixture was concentrated to -5 mL. To the concentrated solution were added 4-(dimethylamino)pyridine (DMAP; 0.04 mmol), B u NF-AlzOs (1.0g, 0.1 mol of B d F in 100 g of & 0 3 ) , and Me1 (2mmol). The reaction mixture was stirred for 12 h and then fdtered. The filtrate was column-chromatographed on silica gel, eluting with ethyl acetatehexane (vlv, 1:lO). The yield (entry 4 in Table 5) was 63 mg (60%). Mp: 143 "C. IR: YCO 1928,1859cm-l. lH NMR (CDCl3): 6 7.54-7.32(m, Ph), 5.17 (t, 5.37 Hz, H3), 3.99 (d, 5.37 Hz, H2), 3.84 (4, 6.59 Hz, H4), 3.43(s, OCH3), 3.02(quint, 6.35 Hz, H6), 2.14 (t, 6.35 Hz, H5), 0.46 (d, 6.35 Hz, CH3) ppm. Anal. Calcd for C2&6Mn03P: C, 67.75;H, 5.28. Found C, 67.62;H, 5.27. (2)Typical procedure when the electrophile was acetic anhydride: PhMgBr (1.2 mmol, 0.4 mL of 3 M solution in diethyl ether) was added dropwise to the solution of 3(P(OMe)3) (0.13g, 0.4 mmol) in 15 mL of CHzClz at 0 "C. m e r 30 min, excess acetic anhydride was added and the resultant mixture stirred for 1 h at room temperature. The reaction mixture was quenched with water and extracted with diethyl ether. The ether extracts were dried over anhydrous MgS04 and evaporated to give a yellow residue. Purification by column chromatography (etherhexane, v/v, 15) gave 0.15g of the product (85%) (entry 17 in Table 5). Mp: 76 "C. IR: vco 1947,1881 cm-', vc-0 1726 cm-'. lH NMR (CDC13): 6 7.20-7.13 (m, 3 H, Ph), 7.05-7.00(m, 2 H, Ph), 5.21(tt,5.2,1.5Hz, H3), 5.155.10(m, H2), 4.65 (q, 5.5 Hz, H4),4.48(d, 6.3Hz, H6), 3.60(d, 11.5Hz, P(OMe)3),3.40(t, 6.4Hz, H'), 2.02(s, CH3) ppm. Anal. Calcd for C1gHzzMn07P: C, 50.91;H, 4.95.Found: C, 50.90; H, 5.14. Characterization of Entry 1 in Table 5. IR: YCO 2004, 1912 cm-'. lH NMR (CDCI3): 6 5.43(td, 5.37,1.47Hz, H3), 4.73(t,5.86Hz, H4), 3.96(d, 5.37Hz, H2),3.39(9, OCH3), 3.13 (t, 5.13 Hz, H5),3.13-3.04(m, H6),0.63(d, 6.34Hz, CH3) ppm. HRMS: mlz (M+)calcd 262.0038,obsd 262.0250. Characterization of Entry 2 in Table 5. IR: YCO 2008, 1932 cm-l, YC-0 1744 cm-l. lH NMR (CDC13): 6 5.56(td, 5.41,
1.67 Hz, H3), 5.06(d, 5.77 Hz, H2),4.67 (t, 5.57 Hz, H4), 3.40 (td, 6.27,1.68 Hz, H'), 3.30-3.06 (m, H6), 2.37 (q, 7.55 Hz, CHz), 1.16 (t, 7.71Hz, CHzCHs), 0.55 (d, 6.23 Hz, CH3) ppm. HRMS: mlz (M+)calcd 304.0143,obsd 304.9900. Characterization of Entry 3 in Table 5. IR: YCO 2004, 1926 cm-l, Y C 1749 ~ cm-'. 'H NMR (CDCl3): 6 5.55(td, 5.40, 1.72Hz,H3), 5.04 (d, 5.81Hz, H2),4.67(t, 5.64Hz, H4), 3.41 (t, 5.65Hz, H'), 3.20-2.90 (m, H6), 2.13 (9, CH3), 1.80-0.80 (m, C&) ppm. HRMS: mlz (M+) calcd 332.0456,obsd 332.0475. Characterization of Entry 5 in Table 5. Mp: 174 "C. IR: vco 1917,1850cm-l. lH NMR (CDC13): 6 7.57-7.25 (m, 15 H, Ph), 5.16 (t, 5.34Hz, H3), 3.91(d, 5.86Hz, H2), 3.84(q, 6.17Hz, H4), 3.58(9, 6.83 Hz, OCHZCH~), 3.04-2.95 (m, H6), 2.12(t, 6.59Hz, H'), 1.31(t, 7.08 Hz, OCHZCH~), 0.45(d, 6.59 Hz, CH3) ppm. HRMS: mlz (M+) calcd 510.1157, obsd 510.1294. Characterization of Entry 6 in Table 5. Mp: 145 "C dec. IR: YCO 1928,1860cm-l. lH NMR (CDC13): 6 7.60-7.32 (m, 15 H, Ph), 5.98(ddd, 16.35,10.49,5.84Hz, HC),5.37(dd, 17.09,1.47Hz, Ha), 5.23(dd, 10.50,1.47Hz, Hb), 5.16 (t, 5.61 Hz, H3), 4.21-4.01 (m, OCHz), 3.98(d, 5.13 Hz, H2), 3.82 (q, 5.37 Hz, H4), 3.05 (quin, 5.86Hz, H6), 2.14 (t, 5.37Hz, H'), 0.47(d, 6.35Hz, CH3) ppm. We indicated the proton attached to the carbon bearing CHzO as HC,the proton tram to Hc as Ha and the proton cis to Hc as Hb. HRMS: mlz (M+) calcd 522.1156,obsd 522.1271. Characterization of Entry 7 in Table 5. Mp: 185 "C. IR: YCO 1933,1870 cm-l, YC=O 1747 cm-l. lH NMR (CDC13): 6 7.53-7.34 (m, 15 H, Ph), 7.19-7.10(m, 3 H, Ph), 6.93-6.89 (m, 2 H, Ph), 5.16-5.09(m, H2z3),4.38(d, 5.9 Hz, H6), 4.11(m, 6.3Hz, H4),2.83 (t,6.3Hz,H6), 2.01(s, CH3)ppm. Anal. Calcd for C33H2&h04P: C, 69.93;H, 4.81. Found: C, 69.43;H, 5.52. Characterization of Entry 8 in Table 5. Mp: 76 "C. IR: YCO 1947,1881 cm-'; YC-0 1745 cm-l. lH NMR (CDC13): 6 7.55-7.34(m, 15 H, P P h ) , 7.19-7.17(m, 3 H, Ph), 6.936.86 (m, 2 H, Ph), 5.29-5.10 (m, H2,3),4.38 (d, 5.4 Hz, H6), 4.11(q, 5.37Hz, H4),2.81(t, 6.3 Hz, H5), 2.30(9, 7.3 Hz, CHzCH3), 1.08 (t, 7.6 Hz, CHzCH3) ppm. Anal. Calcd for C35H30Mn04P:C, 70.0;H, 5.04. Found: C, 70.6;H, 5.07. Characterization of Entry 9 in Table 5. Mp: 83 "C. IR: YCO 1945,1881 cm-l; YC-0 1761 cm-l. 'H NMR (CDC13): 6 5.85-5.79 (m, H3), 4.62 (q, 7.07Hz, H4),3.59 (d, 11.23Hz, P(OMe)3), 2.93 (br d, 6.35 Hz, H2), 2.82 (dd, 12.20,5.61 Hz, Hendo),2.47 (m, H5),2.24(dd, 12.70,6.59Hz, Ha"), 2.14(s, CH3) ppm. HRMS: mlz (M+)calcd 372.0112,obsd 372.0171.
Organometallics, Vol. 14, No. 2, 1995 1025
Chemistry of [(r16-C~~OH)Mn(C0)37C10*
02') could be generated. All the hydrogen atoms could be Characterization of Entry 10 in Table 5. IR: YCO 1931, located by difference Fourier synthesis and refined isotropically 1864 cm-l. lH NMR (CDCl3): 6 5.20 (t, 5.63Hz, H3), 4.47 (9, in the final refinement. The last cycle of refinement converged 5.86Hz, H4),3.92(d, 5.61Hz, H2),3.54(d, 11.23Hz, P(OMe)s), with R(F)= 0.0277and w R ( F )= 0.0728.Crystal data, details 3.41 (s, OCHs), 3.20-3.05 (m, H6), 2.80(t, 5.68 Hz, H6), 0.56 of the data collection, and refinement parameters are listed (d, 6.31Hz, CH3) ppm. HRMS: mlz (Mf) calcd 358.0378,obsd in Table 1. The final atomic parameters are given in Table 2. 358.0380. Characterization of Entry 11 in Table 5. IR: YCO 1945, X-ray Structure of a(PPh3). Single crystals suitable for 1883 cm-'. lH NMR (CDC13): 6 5.96(ddd, 17.1,10.5,5.6Hz, X-ray analysis were obtained by slow evaporation of a CHZHC), 5.33(dq, 17.3,1.7Hz, Ha), 5.24(dq, 10.5,1.5Hz, Hb), 5.20 Clhexane (vlv, 2:l)solution of 2(PPh3). The crystal was (tt, 5.37,1.71 Hz, H3), 4.46 (9, 5.13 Hz, H4), 4.18-3.96 (m, mounted on a Rigaku AFC4 diffractometer, and the unit cell OCHz), 3.93(d, 5.61Hz, H2),3.55 (d, 11.2Hz, P(OMe)3), 3.12 parameters were obtained from a least-squares fit of the 22 (quint, 6.35 Hz, H6), 2.81(tt, 6.35,1.95Hz, H5), 0.58 (d, 6.35 centered reflections (8.95"< 28 < 11.39'). Data were collected Hz, CH3) ppm. HRMS: mlz (M') calcd 384.0534,obsd with Mo Ka radiation by using an wl28 scan mode. The crystal 384.0526. structure was solved by the use of the conventional heavyCharacterizationof Entry 12 in Table 5. Mp: 56 "C. atom method as well as difference Fourier technique and I R YCO 1950,1888 cm-'. 'H NMR (CDC13): 6 5.20(tt, 5.37, refined by means of full-matrix least-squares F using 1.71 Hz, H3), 4.40(m, 5.12 Hz, H4), 3.98 (d, 5.37Hz, H2),3.54 SHELXL93. Non-hydrogen atoms were found by S H E U S 8 6 (d, 11.47Hz, P(OMe)3),3.05 (quint, 5.63Hz, H6),2.79(tt,5.86, and refined anisotropically; all the hydrogen atoms were 1.95 Hz, H5), 0.53 (d, 6.35Hz, CH3), 0.26(s, SiMea), 0.11(s, refined by difference Fourier synthesis. All the hydrogen t-C4H9)ppm. LRMS: mlz (M+) calcd 458,obsd 458. atoms were ridden t o the bonded atoms with the isotropic Characterizationof Entry 13 in Table 5. Mp: 72 "C. displacement parameters fured with the value of 1.2 times IR: YCO 1944,1878 cm-l, vc-0 1752 cm-l. 'H NMR (CDCl3): those of the bonded atoms. The last cycle of refinement 6 5.35 (t, 5.13Hz, H3), 4.83(d, 5.37Hz, H2), 4.48-4.46 (br m, converged with R(F) = 0.0657 and w R ( F )= 0.1394. Crystal H4), 3.56 (d, 11.2Hz, P(OMe)S), 3.14-3.11 (m, H5s6),2.10 (s, data, details of the data collection, and refinement parameters C(0)CH3), 0.47 (d, 5.86 Hz, CH3) ppm. Anal. Calcd for are listed in Table 1. The final atomic parameters are given C14H20Mn0,P: C, 43.54;H, 5.22. Found: C, 43.40;H, 5.70. in Table 3. Characterization of Entry 14 in Table 5. IR: YCO 1944, X-ray Structure of 3. Single crystals suitable for X-ray 1878 cm-l, vc-0 1748 cm-l. lH NMR (CDC13): 6 5.34 (t, 5.61 analysis were obtained by slow evaporation of a solution of Hz, H3),4.83(d, 5.61 Hz, H2), 4.47(m, H4), 3.56 (d, 11.2 Hz, hexane. X-ray data were collected on Enraf-Nonius CAD4 P(OMe)3), 3.15-3.07 (m, H5s6),2.37 (9, 7.16Hz, CHz), 1.15 (t, diffractometer using Mo K a radiation at room temperature. 7.57 Hz, CHzCH3), 0.46(d, 5.86Hz, CH3) ppm. HRMS: mlz Cell parameters and orientation matrix for data collection were (M+)calcd 400.0484,obsd 400.0484. obtained from least-squares refinement using the setting Characterizationof Entry 15 in Table 5. I R YCO 1945, angles of 25 reflections in the range 20.90' < 28 < 28.80'. The 1880 cm-l, vc-0 1742 cm-l. 'H NMR (CDC13): 6 5.32(t, 5.4 structure was solved by Patterson methods using SHEIX86 Hz, H3), 4.92-4.88 (m, H2),4.49(t, 6.4Hz, H4), 3.56 (d, 11.2 and refined by full-matrix least-squares methods. NonHz, P(OMe)3),3.17-3.03(m, H5l6), 2.36 (9, 7.6 Hz, CHz), 1.15 hydrogen atoms were refined anisotropically. While 11 hy(t, 7.6Hz, CH3), 1.06-0.79 (m, C4H9) ppm. HRMS: mlz (M+) drogen atoms attached t o carbon atoms (C2,C3, C4,C5, C6, calcd 442.0953,obsd 442.0946. C14,C17)were located from the difference Fourier map and Characterizationof Entry 16 in Table 5. Mp: 90 "C. their positional parameters refined, the positions of other IR: vco 1931,1864 cm-l. lH NMR (CDC13): 6 7.20-7.00 (m, hydrogen atoms were calculated and fured during the refine3 H, Ph), 7.05-7.00 (m, 2 H, Ph), 5.21 (tt, 5.2,1.5 Hz, H3), ment. The isothermal parameters of all the hydrogen atoms 4.66(m, 6.8Hz, H4), 4.31(d, 5.9Hz, H6), 4.12(d, 5.6 Hz, H2), were fixed with 1.3times those of bonded carbon atoms. The 3.59(d, 11.2 Hz, P(OMe)3), 3.44 (s, CH3), 3.07 (tt, 6.4,1.8 Hz, last cycle of refinement converged t o R(F)= 0.038and w R ( n H5) ppm. Anal. Calcd for C17Hz2MnO&': C, 51.44;H, 5.11. = 0.040.All the calculations except for the structure solving Found: C, 51.39;H, 5.81. were performed with the Enraf-Nonius Molen package. CrysCharacterization of Entry 18 in Table 5. IR: YCO 1946, tal data, details of the data collection, and refinement param1883 cm-l, YC-0 1742 cm-l. lH NMR (CDC13): 6 7.22-7.10 eters are listed in Table 1. The final atomic parameters are (m,3H,Ph),6.98-6.94(m,2H,Ph),5.36(t,5.4Hz,H3),5.15given in Table 4. 5.11 (m, H2),4.66(m, 5.5 Hz, H4),4.48 (d, 5.6 Hz, H6), 3.59 (d, 11.2Hz, P(OMe)3),3.38 (t, 6.4 Hz, H5),2.30(q, 7.6 Hz, CHd, Results and Discussion 1.10(t, 7.6Hz, CH3) ppm. HRMS: mlz (M+) calcd 462.0640, obsd 462.0634. Syntheses of 2 and 3. Reaction of 1+ with t-BuOK Oxidation of 3. Complex 3 (L = P(OMe)3, Nu = Ph, E = CH3)in acetone was cleanly and rapidly oxidized by dropwise led to 2(CO) in 93% yield. Single crystals of 2(CO) addition at 0 "C of a slight excess of Jones reagent. Extraction suitable for X-ray studies were grown in solution. 2(CO) with diethyl ether, drying with MgS04, and solvent evaporareacted with several kinds of nucleophiles. When 2(CO) tion gave a 85% yield of pure 2-phenylanisole, identified via was treated with t-BuLi and then with HBF4, [(t-C4H9lH NMR in CDC13: 6 7.57-6.90(m, 9 H, Ph), 3.80(s, OCH3) CsH5)Mn(C0)31BF4was obtained in low yield.g When PPm.s C3H5MgBr or PhCzLi was used as a nucleophile, we X-ray Structure of 2(CO). Single crystals suitable for could only confirm the formation of [(Nu-CsHs)Mn(CO)3]X-ray analysis were obtained by slow evaporation of a CH2BF4 by checking the IR spectra. Due to the low yields, Clhexane (vlv, 2:1) solution of 2(CO). The crystal was we did not pursue the chemistry of 2(CO). We thought mounted on a Rigaku AFC4 diffractometer, and the unit cell that complex 2(CO) was unstable with respect to the parameters were obtained from a least-squares fit of the 34 centered reflections (11.59' < 28 < 36.74'). Data were nucleophilic addition. Thus we focused our efforts to collected with Mo K a radiation by using wl28 scan mode. The find oxocyclohexadienyl complexes that are stable with crystal structure was solved by the use of the conventional respect to nucleophilic addition. We found that the heavy-atom method as well as difference Fourier technique phosphorus-substituted oxocyclohexadienyl complexes and refined by means of full-matrix least-squares fit on F 2(PR3) were stable compared with 2(CO). Thus, addiusing SHELXL93. Non-hydrogen atoms (Cl, C2, C3, C4,C5, C6, 01, 02, 03) were found by SHEIXS86 and refined by (9)Jeong, E.;Chung, Y. K.J. Organomet. Chem. 1992,434, 225. anisotropically and the symmetry-related atoms (CY, C4', C5', ~~
1026 Organometallics, Vol. 14, No. 2, 1995
Lee et al.
Table 1. Crystal Data, Details of the Data Collection, and Refinement Parameters formula fw cryst syst
CsHsMn04 232.07 monoclinic P2l/m (No. 11) 6.968( 1) 9.072(2) 7.131(1) 104.46(2) 11.590 5 2e 5 36.740 436.3 1) 2 1.766 21 0.71069 graphite 14.93 none yellow 0.60 x 0.30 x 0.25 Rigaku AFc4 0/2e 4 1.5 0.35 tan e 232 50 894 825 (Rint = 0.02) 752 [I =- 2u(O] 84 0 d h 5 8,0 d k 5 10, -8 " I 5 8 1.128 0.028 [F > 4u(F)] 0.033 (all data) 0.073 [ F > 4a(F)] 0.076 (all data)
lP(% b (A)
c (A) B (deg)
least-squares fit volume (A31
z
D(calcd) (mg/mm3) temp ("C) 1 (Mo Ka) (A) monochromator abs coeff (cm-I) abs correction cryst color cryst size (mm3) diffractometer scan mode scan speed in o (deg/min) scan range in o (deg) F(0W 28,, (deg) no. of data collcd no.of unique data no. of obsd data no. of variables index ranges goodness of fit
+
WF)" wR(F); wR(F2)'
C19HzzMn07P 448.30 orthorhombic P c u (NO. ~ ~ 29) 26.254(2) 7.625(1) 10.31l(3) 90 20.900 5 28 5 28.80 2604.0(6) 4 1.442 23 0.71073 graphite 7.25 none yellow 0.35 x 0.30 x 0.20 Enraf-Nonius CAD4 o variable 1.0 0.35 tan e ? 50 2121 2121 1350 [I=- 3u(1)] 285 ??? 1.180 0.038 [F > 6u(F)]
+
0.040 [F =- 6u(F)]
C2d2aMnOsP 466.33 orthorhombic Pbca (No. 61) 14.89314) 16.324(8) 17.673(12) 90 8.950 5 2e 5 11.390 4297(6) 8 1.442 19 0.71069 graphite 7.15 none yellow 0.65 x 0.30 x 0.20 Rigaku AFc4 0128 4 1.0 0.35 tan e 1920 50 3287 3787 2311 [ I > 2&4] 280 -17 5 h 5 0,O 5 k 5 19,O 5 I5 20 1.027 0.066 [F > 4u(F)] 0.132 (all data) 0.139 [F > 4a(F)] 0.249 (all data)
+
where w = 4Fo2/[uz(Fo2) + (0.04F02)z]1/2 for C19HzzMn07P. wR(F?) = [Zw(Foz WF)= CllFol - lFcll/ClFol. mF)= [Cw(lFoI - IFcl)2~xWlFol21'~, - Fcz)z/~w(F,2)z]1~2, where w = l/[uz(Foz) + + bP], P = (Fo2 + 2Fc2)/3,u = 0.046, and b = 0.11 for CsHsMn04 and a = 0.066 and b = 16.5 for C~dzoMn03P.
Table 2. Atomic Coordinates ( x 104 for Non-Hydrogens, x l@for Hydro ens) and Equivalent Isotropic Displacement Parameters x 1@ for Non-Hydrogens, x 1@ for
(j2
A2
Hydrogens) for 2(CO)
X
Mn C(1) C(2) C(3) C(4) C(5) C(6) O(1) O(2) O(3) H(4) H(5) H(6)
1005(1) - 190(5) -654(4) 4 198(5) 3638(4) 3397(4) 3298(5) -951(5) -1714(3) 4908(4) 373(5) 321(5) 316(8)
Y
Z
2500 2500 1128(3) 2500 1172(3) 1179(4) 2500 2500 291(3) 2500 31(4) 32(4) 250
1951(1) -625(5) 2480(3) 842(5) 1715(4) 3592(4) 4583(6) -224 l(4) 2872(3) -587(4) 113(4) 421(4) 578(8)
&XI4
27(1) 35U) 36(1) 34( 1) 36( 1) 42( 1 46(1) 57(1) W1) 49U) 4(1) 5(1) 7 ~ )
U, is defined as one-third of the trace of the orthogonalized Uij tensor.
tion of NMO or T W O (1 equiv) and phosphorus donors (3 equiv) to 1+ led to [(CsH50)Mn(CO)z(PR3)1(R = OMe, Ph) (2) in 73% (R = Ph) and 85% (R = OMe) yields, respectively. Both complexes are air-stable orange solids that can be purified by recrystallization and have been characterized by standard spectroscopic and analytical techniques. Single crystals of 2(PPh3) suitable for X-ray studies were grown in solution. 2 reacts consecutively with a nucleophile (Nu) and an electrophile (E) to give reasonable to high yields of double-addition products, [(6-Nu-v5-1-EO-CsH5)Mn(CO12Ll (L = CO, PPh3, P(OMe)3) (3; Scheme 1 and Table 5). The formation of 3 was confirmed by the X-ray study of 3 (L = P(OMe)3, Nu = Ph, E = C(O)CH3).
When the electrophile was an alkyl halide, tetrabutylammonium fluoride impregnated on neutral alumina was added to promote alkylation.1° When we compare the yields of entries 1,4, and 10, the yield of the product is substantially dependent upon the ligand L and increased greatly when L is P(OMe13. However, when we compared the yields of entries 2/14 and 3/13, the yields were almost the same even though the ligands were very different. Comparison of the yields of entries 13/17 and 14/18 shows that the yield was dependent upon the nucleophiles. With the silicon-containing electrophile (entry 121, the yield was rather low due to decomposition during purification. The controlling factors for the yields of 3 are not fully understood. The oxocyclohexadienyl ligand can be used as a precursor for the synthesis of 1,2-disubstituted benzenes. Thus, the 1,2-disubstituted arene was liberated in 85% isolated yield from metal complex 3 (L = P(OMe)3, Nu = Ph, E = CH3) by treatment with Jones reagent, followed by solvent removal and extraction with diethyl ether. Comparison of the lH NMR with literature data verified that the product was 2-phenylani~ole.~ Many methodologies to make 1,2-disubstituted aromatic hydrocarbons are kn0wn.l' However, 1,a-disubstituted benzene precursors are usually needed. Recently, the regioseledive preparation of 1,2-disubstituted benzenes via chromium carbonyls was reported.12 However, these methodologies suffer from the very limited ranges of substrates and side reactions. The double addition to [(CsH50(Mn(C0)2Llcan be done in a one(10)Ando, T.; Yamawaki, J.; Kawate, T.; Sumi, Bull. Chem. SOC.Jpn. 1982, 55, 2504.
s.;Hanafusa, T.
Organometallics, Vol. 14, No. 2, 1995 1027
Chemistry of Nq6-C&~OH)Mn(CO)&!lO4 Table 3. Fractional Atomic Coordinates ( x 104) and Equivalent Isotropic Displacement Parameters (A* x 103) for 2(PPh3) X
316(1) 573(1) -29(4) 2204(3) 1017(4) 104(4) 146l(4) 445(5) 378(5) -336(5) -981(5) -872(5) -151(5) 1423(4) 1707(7) 2378(8) 2786(5) 2550(6) 1874(5) -418(4) -417(5) -1162(5) - 1904(5) - 1918(5) -1184(4) 979(4) 545(5) 917(7) 1711(6) 2140(5) 1779(5)
Y
z
uwa
1027(1) 1752(1) -467(3) 550(3) 1 0 ~ 4 ) 137(4) 756(4) 1128(5) 1904(4) 2082(5) 1496(6) 698(5) 515(5) 2551(4) 2910(5) 3491(6) 3715(5) 3378(5) 2804(5) 2263(4) 3061(4) 3387(5) 2900(5) 2098(5) 1784(4) 1146(4) 1148(6) 712(7) 301(5) 313(5) 728(4)
Ues is defined as one-third of the trace of the orthogonalized Uij tensor.
pot reaction, and Grignard reagents or RLi can be used as nucleophile and alkyl halides or acid anhydrides can be used as electrophiles. Thus, the utilization of oxocyclohexadienyl manganese compounds can be a viable and facile procedure for obtaining 1,2-disubstituted benzenes. Molecular Structures of 2(CO), 2(PPh3), and 3 (L = P(OMeI3, Nu = Ph, E = C(O)CH3). The geometry of 2(CO) along with the atomic numbering scheme is depicted in Figure 1,and bond distances and angles are given in Table 6. A n X-ray diffraction study of 2(CO) confirms the y5-oxocyclohexadieny1 bonding mode. Heppert13reported the synthesis and chemistry of [(y-C6H50)Cr(C0)3]-,defined as an q6-arenebonding mode; however, they did not report an X-ray structural determination. The C-0 bond length of the ketone, 1.239(4) A, is quite similar to the C=O bond distances (11)Tashiro, M.; Fukuda, Y.; Yamoto, T. J . Org. Chem. 1983,48, 1927. Bennetau, B.; Dunogues, J.; Krempp, M. Chem. Abstr. 1990, 113,586892. Sartori, G.; Maggi, R.; Bigi, F.; Arienti, A,; Casnati, G. Tetrahedron Lett. 1992, 33, 2207. Sartori, G.; Maggi, R.; Bigi, F.; Arienti, A.; Casnati, G. J . Chem. Soc., Perkin Trans. 1 1991, 3059. Bigi, F.;Casnati, G.; Sartori, G.; Araldi, G . Gazz. Chim. Ztal. 1990, 120,413. Bigi, F.;Casnati, G.; Sartori, G.; Dalprato, C.; Batolini, R. Tetrahedron Asymmetry 1990,1, 861. Sartori, G.;Casnati, G.; Bigi, F.; Predieri, G. J . Org. Chem. 1990,55, 4371. Mills, R. J.;Snieckus, V. J . Org. Chem. 1983,48, 1565. Gschwend, H. W.; Hamdan, A. J . Org. Chem. 1976,40,2008. Gschwend, H. W.; Rodriguez, C. R. Org. React. (N.Y.)1979,26,1. Puterbaugh, W. H.; Hauser, C. R. J. Org. Chem. 1964,29,853. (12)Blagg, J.; Davies, S. G.; Goodfellow, C. L.; Sutton, K. H. J . Chem. SOC.,Chem. Commun. 1986, 1283. Blagg, J.; Davies, S. G.; Goodfellow, C. L.; Sutton, H. K. J . Chem. Soc., Perkin Trans. 1 1990, 1133. Heppert, J.A.;Aube, J.;Thomas-Miller, M. E.; Milligan, M. L.; Takusagawa, F. Organometallics 1990,9,727.Kundig, E.P.; Amurrio, D.; Liu, R.; Ripa, A. Synlett 1991,657. Kundig, E.P.;Ripa, A.; Liu, R.; Amurrio, D.; Bernardnelli, G. Organometallics 1993,12,3724. (13)Heppert, J. A.;Boyle, T. J.; Takusagawa, F. Organometallics 1989,8,461.
Table 4. Atomic Coordinates and Equivalent Thermal Parameters for 3 (L = P(OMe)3, Nu = Ph, E = C(0)CH3) atom
X
Y
Z
Mn P 01 02 03 04 05 06 07 c1 c2 c3 c4 c5 C6 c7 C8 c9 c10 c11 c12 C13 C14 C15 C16 C17 C18 C19
0.12986(3) 0.07911(7) 0.2 162(2) 0.2 120(2) 0.1413(2) 0.0404(2) 0.1060(2) 0.0275(2) 0.05 19(2) 0.2019(2) 0.2354(2) 0.2002(2) 0.1699(2) 0.1554(2) 0.1731(2) 0.2872(2) 0.3290(2) 0.3750(3) 0.3809(3) 0.3390(3) 0.2924(2) 0.2186(2) 0.2301(3) 0.1376(2) 0.0763(2) 0.0792(8) 0.0292(3) 0.0227(4)
0.2071(1) 0.0813(3) 0.0477(5) -0.1755(5) -0.0965(6) 0.3319(7) -0.0572(6) -0.0572(6) 0.1994(7) 0.1757(7) 0.208l(7) 0.3070(8) 0.4412(8) 0.4480(7) 0.3082(8) 0.2886(8) 0.1809(8) 0.25 18(11) 0.4294(10) 0.5351(9) 0.4682(8) -0.1251(8) -0.2316(8) 0.0155(8) 0.281l(9) -0.1462( 11) -0.1498(11) 0.3456(13)
0.000 -0.1383(2) -0.2003(4) -0.0582(4) 0.1738(5) 0.1427(6) -0.2294(5) -0.2294(5) -0.2465(6) -0.1089(6) 0.0090(7) 0.0981(6) 0.0484(6) -0.0825(6) -0.1604(6) -0.022 l(6) -0.0404(7) -0.0743(9) -0.0899(8) -0.0728(8) -0.0395(6) -0.1659(6) -0.2799(7) 0.01021(6) 0.0892(8) -0.3309(8) -0.ooo8(8) -0.2174(14)
Be,"
(AZ)
2.97(1) 3.98(4) 2.89(8) 4.0(1) 5.7(1) 6.9(1) 5.0(1) 6.3(1) 7.7(2) 2.8(1) 2.8(1) 3.0(1) 3.6(1) 3.2(1) 3.0(1) 3.0(1) 4.3(2) 5.8(2) 5.3(2) 4.8(2) 3.9(2) 3.0(1) 4.9(2) 3.7(1) 4.3(2) 6.7(2) 8.6(2) 12.3(4)
Table 5. Yields of Compounds 3 entry
L
1" 20 36 40 5" 6" 7b 8b
9b lo" 110 12b 13b 14b 15" 16" 17b 186
Nu
E
yield (%) 58 49 59 60 55 49 55 50 68 84
64 49 58 45 84 52 85 70
DME was used as a solvent. CH2C1.2 was used as a solvent
of 6- or y-lactams,14and the Mn-C3 distance, 2.540(3)
A, is quite long and reflects the absence of a significant
bonding interaction. However, the dihedral angle (21.3") between a plane C4-C5-C6-C5'-C6' and a plane of C4-C3-C4' is quite small compared to those in other cyclohexadienylmanganesecomplexes: 43" in [(q5-C&)Mn(C0)3],1541" in [{y5-(C2H502C)2CH-CsH6}Mn(CO)31,16 36.5" in [(q5-PhCsH6)Mn(C0)31,'739.6" in [(y5-PhC6H6)Mn(C0)2NOlBF4,1739.6" in [{(q5-C5H4)W(CO)3CH3}q5-C6H5]Mn(C0)3,1s and 38.0" in [((C2H50)2P(0)-q5C6H6}Mn(C0)31.19 Thus, we expect that there should (14)Allen, F. H.; Kennard, 0.;Watson, D. G.; Brammer, L.; Orpen, A. G.; Taylor, R. J . Chem. Soc., Perkin Trans. 2 1987,S1. (15)Churchill, M. R.; Scholer, S. Znorg. Chem. 1969,8,1950. (16)Mawby, A.;Walker, P. J. C.; Mawby, R. J. J . Organomet. Chem. 19'73. _ _ .55. _ (2.79. , - - I
(17)Ittel, S. D.; Whitney, J. F.; Chung, Y. K.; Williard, P. G.; Sweigart, D. A. Organometallics 1988,7, 1323. (18)Chung, T.-M.; Chung, Y. K. Organometallics 1992,11, 2822.
1028 Organometallics, VoE. 14,No. 2, 1995
Lee et al.
Figure 1. Structural drawing and atomic numbering
scheme for complex Z(C0).
Figure 2. Structural drawing and atomic numbering
scheme for complex Z(PPh3).
Table 6. Selected Bond Distances (A) and Angles (deg) for 2(CO), 2(PPhd, and 3 Mn-C( 1) Mn-C(6) C(3)-C(4) Mn -C(2) C( 1)-O(1) C(4)-C(5) Mn-C( 1)-O( 1) C(3)-C(4)-C(5) Mn-C(2)-0(2) Mn -C( 1) Mn-C(6) C(4)-C(5) C(8)-C(3) Mn-C(2) Mn-P CO)-C(6) O(l)-C( 1) Mn-C(l)-O( 1) P-Mn-C( 1) C(5)-C(4)-C(3) Mn-C(2)-O(2) P-Mn-C(2) Mn -C( 1) Mn -C(6) C(1)-0(1) Mn-C(3) Mn-P C(13)-0(2) C(l)-c(2)-c(3) C(4)-C(5)-C(6) Mn-C( 15)-0(3) C(2)-C(3)-C(4) C(5)-C(6)-C( 1)
Compound 2(CO) 1.817(4) Mn-C(4) 2.140(4) C(2)-0(2) 1.453(3) CG)-C(6) 1.801(3) Mn-C(5) 1.142(4) C(3)-0(3) 1.390(4) 179.6(3) 121.2(3) 177.4(2)
C(4)-C(5)-C(6) C(4)-C(3)-0(3) C(5)-C(6)-C(5’)
Compound 2(PPh3) 1.773(7) Mn-C(4) 2.153(7) C(3)-0(3) 1.387(10) C(6)-C(7) 1.435(10) 0(2)-C(2) 1.769(6) Mn-C(5) 2.277(2) C(3)-C(4) 1.401(11) C(7)-C(8) 1.1#(8) 175.4(6) 90.0(2) 122.4(7) 177.2(6) 92.6(2)
C(6)-C(5)-C(4) C(l)-Mn-C(2) C(4)-C(3)-0(3) C(7)-C(6)-C(5)
Compound 3 2.212(6) Mn-C(4) 2.149(6) Mn-C(l5) 1.408(7) C(2)-C(7) 2.240(6) Mn-C(5) 2.175(2) Mn-C( 16) 1.189(8) 102.4(4) 115.4(5) 175.1(6) 119.5(5)
Mn-C(16)-O(4) C(3)-C(4)-C(5) C(6)-C(l)-C(2) P-Mn-C(16)
2.236(3) 1.142(3) 1.402(4) 2.147(3) 1.239(4) 121.5(3) 123.9(2) 117.5(4) 2.267(6) 1.238(8) 1.425(11) 1.165(7) 2.179(7) 1.463(10) 1.39310)
0
122.3(7) 90.9(3) 122.9(7) 116.6(7)
2.131(6) 1.806(6) 1.528(7) 2.132(6) 1.771(7) 177.2(7) 122.4(6) 120.7(5) 89.7(2)
be a small contribution of the y6-phenoxide bonding mode in the structure. The cyclohexadienyl ring shows a ring slippage toward C5-C6-C5’ (the average distance of Mn-C5, Mn-C6, and Mn-C5’ is 2.14 A and the bond distance of Mn-C4 is 2.236 A).zo The geometry of 2(PPh3) along with the atomic numbering scheme is depicted in Figure 2, and bond (19)Lee, T.-Y.; Yu, H.-K. Bae; Chung, Y. K.; Hallows, W. A.; Sweigart, D. A. Zrwrg. Chim. Acta 1994,224,147. (20) Lee, Y.-A.; Chung, Y. K.; Kim, Y.; Jeong, J. W.; Chung, G.; Lee, D.Organometallics 1991,10, 3707.
Figure 3. Structural drawing and atomic numbering scheme for complex 3 (L = P(OMe)3,Nu = Ph, E = C(0)CH3).
distances and angles are given in Table 6. An X-ray diffraction study of 2(PPh3) also confirms the y5-oxocyclohexadienyl bonding mode. The geometric parameters of 2(PPh3) are in agreement with those found in 2(CO). The C-0 bond length of the ketone is 1.238(8) 8, and the Mn-C3 distance, 2.494(7) A, is quite long and reflects the absence of a significant bonding interaction. However, the dihedral angle (14.3”)between a plane of C4-C5-C6-C7-C8 and a plane of C4-C3-C8 is quite small compared to those in other cyclohexadienylmanganese complexes. When we compared the dihedral angle of 2(PPh3) to that of Z(CO), the dihedral angle decreased as the electron density of the metal center increased. Thus, we expected that the contribution of the y6-phenoxide bonding mode would increase in 2(PPh3) compared to that of 2(CO). However, the bond distances of Mn-C3 and C3-03 in 2(CO) and 2(PPh3) were not as sensitive as the dihedral angles.
Chemistry of [(r16-C~~OH)Mn(CO)dC10~ The geometry of 3 (L = P(OMe)3, Nu = Ph, E = C(0)CH3) along with the atomic numbering scheme is depicted in Figure 3, and bond distances and angles are given in Table 6. The geometric parameters of 3 are in agreement with those found in other compounds such [q5-Ph-C6H61Mnas [r5-(C~H5C0~)2CH-C6H61Mn(C0)3,16 and [{q5(CO)3,17[{~5-exo-(Me0)2P(0)-CsHs)]Mn(co)3,19 end0-(Et0)2P(O)-C6H6)lMn(C0)3.~~ The cyclohexadienyl ring is nearly planar (with a maximum deviation of 0.008 A). The cyclohexadienyl ring is folded about with an angle of 37.8". The manganese atom is located 1.692 A from the cyclohexadienyl ring. It has been demonstrated that the (oxocyclohexadienyllmanganese complex, generated by the deprotonation of the phenolmanganese complex, provides a useful system for preparing disubstituted cyclohexadienylmanganese derivatives. We are continuing t o explore the use of the (oxocyclohexadieny1)manganesecomplex t o make new (arene)Mn(C0)3+complexes. Extension of
Organometallics, Vol. 14,No. 2, 1995 1029 this chemistry to (/?-naphthol)Mn(C0)3+and [(2,6-disubstituted phenol)Mn(C0)31+cation is also currently underway in our laboratory.21
Acknowledgment. We are grateful to the Korea Science and Engineering Foundation and the Ministry of Education, Republic of Korea (BSRI 94-313). Supplementary Material Available: Tables of atomic positional parameters, thermal parameters, and bond distances and angles for 2(CO), 2(PPh3), and 3 (L = P(OMe)3, Nu = Ph, E = C(O)CH3)(7 pages). This material is contained in many libraries on microfiche, immediately follows this article in the microfilm version of the journal, and can be ordered from the ACS; see any current masthead page for ordering information. OM940700A (21)Lee, S. G.; Lee, S. S.; Lee, T. Y.; Chung, Y. K. Manuscript in preparation.
