Organometallics 1986, 5, 25-33 imparts an eminent reactivity to its contact ion pairs. For example, even when present in such small amounts so as not to be spectroscopically observable, the contact ion pairs of Lif are indicated by greatly enhanced ligand lability (Li+HFe(CO),- W O rapid CO exchange). The substitution reaction is funneled through highly reactive contact ion pairs.
+
-
Acknowledgment. A grant from the National Science Foundation (CHE-8304162) supported this work. Helpful discussions with D. J. Darensbourg and K. H. Whitmire are appreciated. Registry No. PPn+HFe(C0)3P(OMe)3-, 93303-97-0;Na+HFe(CO),P(OMe),-, 98942-46-2;Li+HFe(CO),P(OMe) ~.OCT(IF~I); RF = 2.3% and RwF= 2.7% for those 2431 data with lFol > 6.0a(lFol)]. Final positional parameters are collected in Table V. Anisotropic thermal parameters (Table VS) and a table of observed and calculated structure factor amplitudes appear as supplementary material. Preparations. W(CCMe3)(OZCCMe,),. Pivalic acid (1.84 g, 18.0 mmol) was added to a solution of W(CCMe3)(CH2CMe3), (2.80 g, 6.00 mmol) in pentane (100 mL) that had been cooled to -30 "C. After the solution had warmed to room temperature, the solvent was removed in vacuo. The residue was recrystallized from pentane at -30 "C to give large colorless crystals (3.10 g, 93%): 'H NMR b 1.19 (br s, 9, 02CCMe3), 1.12 (br s, 18, 02CCMe3),1.05 (CCMe,);'% NMR (330K) 6 285.5 (CCMe3),49.4 (CCMe,), 40.4 (02CCMe3),31.3 (CCMe3), 26.0 (02CCMe3). The 02CCMe3resonance was not found. Anal. Calcd for WC20H3606:
+
(20) Nowacki, W.; Matsumoto, T.; Edenharter, A. Acta Crystallogr. 1967, 22, 935. (21) "Syntex XTL Operations Manual", 2nd ed.; Syntex Analytical Instruments Cupertino, CA, 1976.
(22) "International Tables for X-Ray Crystallography";Kynoch Press: Birmingham, England, 1974; Vol. 4, pp 99-101, 149-150. (23) Churchill. M.R. Znorg. Chem. 1973, 12. 1213.
Organometallics, Vol. 5, No. 1, 1986 31
Molybdenum a n d Tungsten Neopentylidyne Complexes Table V. Final Atomic Parameters for W[C~(CM~~)E~ZI(OZCM~)~ atom
X
V
z
0.26592 (3) 0.28291 (49) 0.28578 (47) -0.02443 (47) 0.06943 (52) 0.56184 (50) 0.43616 (54) 0.28902 (65) 0.2975 (11) -0.06157 (76) -0.2510 (10) 0.58107 (79) 0.7614 (13) 0.25006 (76) 0.15598 (83) 0.34786 (81) 0.2412 (12) 0.2126 (20) 0.0732 (24) 0.4218 (23) -0.0124 (14) -0.0176 (19) 0.5070 (14) 0.4942 (20) 0.302 (12) 0.388 (15) 0.207 (10) -0.252 (12) -0.281 (13) -0.355 (13) 0.786 (20) 0.852 (12) 0.722 (15) 0.2036 0.3100 0.0995 0.0659 -0.0344 0.0905 0.4145 0.4399 0.5203 -0.1194 -0.0210 -0.1236 0.0886 -0.0098 0.6191 0.5321 0.6114 0.4004 0.4874
0.21317 (3) 0.39909 (54) 0.45362 (49) 0.41675 (50) 0.20542 (57) 0.12027 (59) -0.00329 (56) 0.50277 (74) 0.6787 (10) 0.34273 (85) 0.4203 (12) 0.00411 (85)
0.18668 (1) 0.07259 (22) 0.19079 (22) 0.20336 (23) 0.12828 (23) 0.16168 (29) 0.11347 (24) 0.11403 (34) 0.07636 (56) 0.15642 (34) 0.13454 (54) 0.11677 (37)
- n.. i_i_i A _ _ (1.51
0.16747'7%) 0.08122 isgj -0.00688 (79) 0.2516 (10) 0.1320 (14) 0.4382 (13) 0.2629 (23) 0.0503 (15) -0.0846 (19) -0.1889 (12) -0.3059 (17) 0.736 (13) 0.664 (15) 0.755 (10) 0.472 (13) 0.330 (15) 0.544 (15) -0.201 (22) -0.049 (12) -0.074 (16) 0.1843 0.0127 0.1211 0.4955 0.4274 0.5139 0.3188 0.3386 0.1470 0.1663 0.0122 -0.1013 -0.1983 -0.0442 -0.1672 -0.2535 -0.4192 -0.3336 -0.2474
0.n72.57 -.- . - - . (721
0.31367 ii;i 0.28998 iSSj 0.28330 (36) 0.38356 (40) 0.46517 (46) 0.38276 (58) 0.37878 (61) 0.32069 (52) 0.27728 (94) 0.29384 (61) 0.3716 (10) 0.1138 (59) 0.0422 (71) 0.0452 (46) 0.0775 (60) 0.1481 (63) 0.1586 (61) 0.086 (10) 0.0681 (57) 0.0249 (74) 0.5106 0.4663 0.4693 0.4274 0.3865 0.3330 0.4239 0.3294 0.3797 0.3110 0.3774 0.2967 0.2862 0.2197 0.2878 0.2491 0.3726 0.3768 0.4155
C, 43.18; H, 6.52. Found: C, 42.92; H, 6.66. Mo(CCMe,)(O,CCMe,),. Pivalic acid (0.40 g, 3.92 mmol) was added as a solid to a solution of yellow Mo(CCMe,)Np, (0.50 g, 1.32 mmol) in pentane (-30 mL) that had been cooled to -30 "C. No color change or precipitate was visible upon addition of the acid. The solution was allowed to warm to room temperature over the next 3 h. The solvent was removed in vacuo to give Mo(CCMe3)(O2CCMe3),as an off-white powder (0.56 g, go%), which was pure by NMR and could be used without further purification in subsequent reactions. An analytical sample (white powder) was prepared by cooling a solution of it in pentane to -30 "C (-30% recovery), followed by a double sublimation a t 60 "C (0.1 pm): 'H NMR 6 1.20 (br s, 27, 02CCMe3),0.94 (CMe,); 13C NMR 6 311.3 (CCMe,), 196.8 (OZCCMe3),53.1 (CCMe,), 40.0 (02CCMe3),27.3 (CCMe,), 26.3 (02CCMe3). Anal. Calcd for MoCzoH3606: c, 51.28; H,7.75. Found: C, 50.63; H, 7.88. W(CCMe3)(O2CCHMe2),. Isobutyric acid (900 pL, 9.70 "01) was added to a solution of W(CCMe3)(CHZCMe3),(1.50 g, 3.22 mmol) in pentane (50 mL) that had been cooled to -30 "C. The solution was warmed to room temperature, and the solvent was removed in vacuo. The resulting white powder was recrystallized from pentane at -30 "C (two crops, 1.40 g, 85%): 'H NMR 6 2.29
(br, 3, O2CCHMe&, 1.09 (s,9, CCMe,), 1.04 (br d, 18, O,CCHMe,); 13C NMR 6 298.2 (JCW= 244 Hz, CCMe,), 199.8 (02CCHMe2), 43.0 (CCMe3),28.7(O2CCHMe2),23.4(Me),8.8 (Me). Anal. Calcd for WC1,H3,,06: C, 39.70; H, 5.88. Found: C, 39.42; H, 5.70. Mo(CCMe3)(O2CCHMe2),. Isobutyric acid (735 pL, 7.93 mmol, 3 equiv) was added all a t once via syringe to a stirred solution of Mo(CCMe3)Np3(1.00g, 2.64 mmol) in pentane (-75 mL) that had been cooled to -30 "C. The reaction was allowed to warm to room temperature over a period of 2 h. Solvents were removed in vacuo, and the resulting off-white solid was crystallized from a minimum amount of ether a t -30 "C to give pale yellow crystals (0.80 g, three crops, 71%): 'H NMR 6 2.41 (sept, O2CCHMe2),1.07 (d, 02CCHMe2),0.94 (CMe,); 13CNMR 6 311.2 (CCMe,), 195.1 (02CCHMe2),51.5 (CMe,), 36.0 (02CCHMe2),27.3 (CMe,), 18.0 (02ccH.kfe2). Anal. Calcd for MoCl,H,06: C, 47.89; H, 7.09. Found: C, 48.17: H. 7.18. W(CCMed(O,CCH,),. Acetic acid (1.11mL. 19.4 mmol) was . added dropwise over -a" period of 3 min to 'solution of W(CCMe3)(CH2CMe3),(3.00 g, 6.43 mmol) in pentane (75 mL) that had been cooled to -30 "C. W(CCMe,)(O2CCH3), began precipitating toward the end of the addition. The precipitate was filtered and dried in vacuo. The product was pure by 'H NMR (2.40 g, 87%): 'H NMR 6 1.63 (br s, 9, 02CCH3),1.13 (s, 9, CCMed; 13CNMR 6 286.5 (CCMe,), 189.1 (O,CMe), 49.6 (CCMe,), 31.4 (Me), 22.7 (Me). Mo(CCMe3)(02CCH3),. Acetic acid (450 pL, 10.6 mmol) was added all at once via syringe to a solution of Mo(CCMe,)Np, (1.00 g, 2.64 mmol) in pentane (-75 mL) that had been cooled to -30 "C. The color of the solution immediately changed to a lighter yellow. The solution was allowed to warm to room temperature over a period of 2.5 h. Removing the solvent in vacuo yielded the product as an off-white powder (0.75 g, 83%): 'H NMR 6 1.80 (br s, 9, O,CMe), 1.00 (CMe,); 13C NMR 6 312.4 (CCMe,), 188.9 (O2CMe), 53.3 (CMe,), 27.3 (CMe,), 22.5 (0,CMe). W(CCMe3)(OZCCF3),(dme). Trifluoroacetic acid (1.49 mL, 19.3 mmol) was added to a solution of W(CCMe3)(CH2CMe3), (3.00 g, 6.43 mmol) and dimethoxyethane (2.00 ml, 19.2 mmol) in pentane (150 mL) a t 0 "C. The product precipitated from solution as red microcrystals (4.00 g, 91%): 'H NMR (CD,Cl,) 6 4.98 (s, OCH3),4.18 (m, OCH,), 3.16 (m, OCH,), 3.45 (s, OCH,), 1.04 (s, CCMe,); 13C NMR (CD2C1,) 6 319.7 (CCMe,), 161.6 (4, J C F = 39 Hz, OzCCF3), 116.3 (q, JCF = 289 Hz, 02CCFJ, 116.0 (q,Jm = 289 Hz, 02CCF3),80.3(OCH,), 79.3 (OCH,), 70.6 (OCH,), 60.6 (OCH,), 50.1 (CCMe,), 33.2 (CCMe,). Anal. Calcd for WC15H19F908: C, 26.41; H, 2.81. Found: C, 26.33; H, 2.80. Mo(CCMe3)(02CCF3),(dme).Trifluoroacetic acid (2.40 mL, 32.3 "01) was added all at once to a solution of Mo(CCMe,)Np, (4.00 g, 10.6 mmol) and 1,2-dimethoxyethane (2.20 mL, 2 equiv) in pentane at -30 "C. The solution immediately turned red-purple, and a purple solid began to form. This mixture was allowed to warm to room temperature. Three hours later the solvents were removed in vacuo, and the light purple solid thus obtained was recrystallized from a minimum amount of ether a t -30 "C. M o ( C C M ~ ~ ) ( O ~ C C Fwas ~ )obtained ~ ( ~ ~ ~ as ) dark purple cubes (5.85 g, three crops, 93%): 'H NMR 6 3.89 (br s, 3, MeOCH2CHz0Me),2.65-2.63 (br, 5 total,MeOCH,CH,OMe), 2.24 (br s, 2, MeOCH,CH,OMe), 1.07 (CMe,); 13C NMR 6 341.3 (CCMe,), 161.1 (br, CF&Oz), 116.7 (9, JcF = 288 Hz, CFSCO,), 76.4 (br t, JCH = 148 Hz, MeOCH2CH20Me),69.6 (br q, JCH = 141 Hz, MeOCH2CH20Me), 59.4 (br q, J c H = 131 Hz, MeOCH2CHz0Me),56.2 (CCMe,), 28.3 (CCMe3). Anal. Calcd for MoC15H1908F9:C, 30.32; H, 3.22. Found: C, 30.09; H, 3.41. MO[C~(CM~,)R',](O~CCHM~~)~ (R'= Me, Et, Ph). R = Me. 2-Butyne (20 pL, 0.256 mmol, 1 equiv) was added all at once via syringe to a pale yellow solution of Mo(CCMe3)(02CCHMe2),(0.10 g, 0.234 mmol) in pentane (7 mL) a t room temperature. The solution immediately turned red. After 2 h the solvent was removed in vacuo. The resulting dark red oil was pure by N M R 'H NMR 6 2.37 (m, Me2CHC02),2.34 (s, CMe), 1.28 (CMe,), 1.08 (d, 02CCHMe2);'3CNMR 6 192.2 (02CCHMe2),78.2 (CCMe,), 72.5 (CMe), 36.1 (02CCHMe2),33.8 (CCMe,), 31.0 (CCMe,), 18.3 (02CCHMe2),6.1 (CMe). R' = Et. The preparation of Mo[C3(CMe3)Et2](02CCHMe2),, a red oil, was analogous t o t h a t of Mo[C3(CMe3)Mez](OzCCHMe2),: 'H NMR 6 2.91 (m, 4, CCH2CH3),2.37 (sept, 02CCHMe2),1.33 (CMe,), 1.14 (t, CCH2CH3),1.08 (d, O,CCHMe,); I.
32 Organometallics, Vol. 5, No. 1, 1986
Schrock et al.
I3C NMR 6 192.2 (02CCHMe2),79.3 (CCMe,), 77.7 (CEt), 36.1 (C,-Ph), 125.6 (C,-py), 115.6 (9,JCF= 290 Hz, CF,C02), 46.2 (02CCHMe2),33.6 (CCMe,), 31.5 (CCMe,), 18.3 (02CCHMe2), ( m e 3 ) ,31.5 (CMed. And. Calcd for MoC27H2404N2F6: C, 49.86; 16.4 (CCH,CH,), 15.3 (CCH,CH,). H, 3.72. Found: C, 49.90; H, 3.92. R' = Ph. Diphenylacetylene (0.21 g, 1.17 mmol, 1equiv) was MO[C~(CM~~)~](O,CCF~)~(~~~). Me,CC=CH (110 wL, 0.897 added to a pale yellow solution of Mo(CCMe3)(02CCHMe2),(0.50 mmol, 1.1equiv was added all at once to a stirred dark red ether g, 1.17 mmol) in pentane (30 mL). The solution turned dark red solution (40 mL) of Mo(CCMe3)(02CCF3),(dme)(0.50 g, 0.841 over the next 15-20 min. After 5 h the solvent was removed in mmol) at -30 "C. The resulting dark red solution was allowed to warm to room temperature over the next 3 h. The solvent and uacuo, leaving a dark red solid. MO[C,(CM~~)P~,](O~CCHM~~)~ (0.55 g, three crops, 7790 of theory) was crystallized from a CF3C02Hwere removed in vacuo to give a red solid which was minimum amount of ether a t -30 "C as red needles: 'H NMR recrystallized from a minimum amount of a 1:l mixture of ether and dichloromethane a t -30 "C to give red plates (0.30 g, 63%) 6 7.62 (HJ, 7.15 (H,), 6.89 (H,), 2.09 (sept, 02CCHMe2),1.56 (CCMe3),0.86(02CCHMe2);'3CNMR 6 193.4 (OZCCHMe2),133.8 in three crops: 'H NMR 6 3.48 (MeOCH2CH20Me), 3.17 (MeOCH,CH,OMe), 1.68 (CMe,); 13C NMR (CD,Cl,) 6 254.6 (CJ, 131.3 (Clw),128.8 (C,), 128.4 (Cp),82.0 (CCMe,), 72.4 (CPh), 36.6 (02CCHMe2),34.2 (CCMe,), 31.7 (CCMe,), 18.1 (02CCHMe2). (CCMe,), 243.2 (Cp), 155.5 (4, J C F = 38 Hz, CF,C02), 115.7 (4, Anal. Calcd for MoC,,HaO6: 61.58: H, 6.67. Found: c, 62.10; JCF= 290 Hz, CF3C02), 72.6 (MeOCH2CH20Me),65.3 (MeOCH2CH20Me),46.2 (CMe3),31.5 (CMe,). H, 6.92. MO[C~(CM~,)R'~](O,CCM~~)~ (R' = Me, Et, Ph). For R' = Mo[C3(CMe3),](0,CCF3)2(PY)2. Excess pyridine (500 pL, 6.21 Me or E t the dialkylacetylene (1equiv) was added all at once via mmol, 4.9 equiv) was added all at once to a stirred dark red ether syringe to a solution of Mo(CCMe3)(02CCMe3),(0.10 g, 0.213 solution (75 mL) of MO[C~(CM~,)~](O~CCF~),(~~~) (0.71 g, 1.26 mmol) in pentane (7 mL). The solution immediately turned dark mmol) at -30 "C. The resulting red-purple solution was warmed red. After 3 h, the solvent was removed in vacuo, yielding Moto room temperature over the next 2 h. The solvents were removed [C3(CMe3)R'2](02CCMe3)3 quantitatively as a red oil. in vacuo, and the red-purple residue was recrystallized from a minimum amount of a 1:l mixture of ether and dichloromethane R' = Me: 'H NMR 6 2.32 (CMe), 1.31 (CCMe,), 1.19 (02CCMe3);13C NMR 6 193.6 (02CCMe3),78.7 (CCMe,), 71.3 a t -30 "C. Small red-purple crystals (0.64 g, 80%) were isolated in three crops: 'H NMR 6 8.82 (H,-py), 6.82 (H,-py), 6.56 (H,-py), (CCH,), 39.7 (02CCMe3),33.8 (CCMe,), 30.9 (CCMe,), 26.6 1.63 (CMe,); I3C NMR (CD2C1J 6 252.9 (CCMe,), 247.5 (C& 155.3 (02CCMe3),5.9 (CMe). R' = Et: 'H NMR 6 2.87 (m, CCH,CH,), 1.33 (CCMe,), 1.18 (4, 2 J =~37 ~Hz, CFSCO,), 150.6 (C,-py), 139.3 (C,-py), 125.3 (C,-py), 115.8 (9, JCF = 290 Hz, CF3C02),46.1 (CMe,), 31.5 (O,CCMe,), 1.13 (t,CCH2CH3);I3C NMR 6 193.6 (02CCMe3),79.9 (CMe3). Anal. Calcd for M o C ~ ~ H ~ ~C, F47.63; ~ ~ H, ~ N ~ : 4.48. (CCMe,), 76.5 (CEt), 39.7 (02CCMe3), 33.6 (CCMe,), 31.5 Found: C, 47.69; H, 4.29. (CCMe,), 26.7 (CCH,CH3), 15.3 (CCH2CH3). R = Ph. Diphenylacetylene (0.19 g, 1.07 mmol, 1 equiv) was W[C3(CMe3)Et2](OzCMe),. A slight excess of 3-hexyne (400 pL, 3.52 mmol) was added to a suspension of W(CCMe,)(O,CMe), added to a stirred solution of Mo(CCMe3)(02CCMe3),(0.50 g, 1.07 (1.50 g, 3.49 mmol) in ether (25 mL). After 3 h all the starting mmol) in pentane (50 mL) a t 25 "C. The solution turned dark material had dissolved and the solution was a deep red. The red over the next 15 min. After 4 h the solvent was removed in solvent was removed from the solution in vacuo, and the residue vacuo, leaving a red solid. The solid was dissolved in a minimum was recrystallized from pentane at -30 "C (two crops, 1.07 g, 60%): amount of a 1:1 mixture of dichloromethane and ether. Bright 'H NMR 6 4.23 (dq, 2, JHH = 15.2, 7.6 Hz, ~(CHAHBCH,)), 3.94 red needles formed at -30 "C (0.48 g, 7090, three crops): 'H NMR (dq, 2, JHH = 15.2, 7.6 Hz, C(CHAHBCH3)), 1.60 (Me), 1.41 (Me), 6 7.62 (H,), 7.15 (H,J, 6.88 (H,), 1.57 (CMe,), 0.98 (O,CCMe,); 1.25 (t, CCHfie); I3C NMR 6 192.2 (02CMe),76.9 (CCMe,), 73.5 13CNMR 6 194.7 (02CCMe3),133.4 (C,), 130.9 (Ciw), 127.6 (C,), (CEt), 25.8 (Me),25.5 (CCMeJ,14.9 (Me),8.6 (Me), 6.6 (CCH2Me). 127.5 (C,), 80.7 (CCMe,), 71.7 (CPh), 39.8 (OzCCMe3),33.6 Anal. Calcd for WCl,H2806: c, 39.86; H, 5.51. Found: C, 39.64; (CCMe,), 31.2 (CCMe,), 26.1 (O,CCMe,). Anal. Calcd for H , 5.54. MOC34H4606: 63.15; H, 7.17. Found c, 63.08; H, 6.82. Mo[C3(CMe3)(Ph)](02CCF3),(dme). Phenylacetylene (190 W[C3(CMe3)Me2](02CCMe3)3. 2-Butyne (141 pL, 1.80 mmol) fiL, 1.73 mmol, 1 equiv) was added all a t once via syringe to a was added to a solution of W(CCMe3)(02CCMe3),(1.00 g, 1.80 solution of M o ( C C M ~ ~ ) ( O , C C F ~(1.00 ) ~ ( g, ~ ~1.68 ~ ) mmol) in mmol) in pentane (15 mL). The color of the solution slowly ether (60 mL) a t -30 "C. The solution immediately darkened to changed to deep red over a period of 4 h The solvent was then purple-red. The solution was allowed to warm to room temremoved in vacuo and the residue recrystallized from pentane at perature. After 2 h the solvent was removed in vacuo, leaving -30 "C to give large red prisms (two crops, 0.68 g, 62%): 'H NMR a purple-red solid. Mo[C,(CM~,)(P~)](O,CCF~)~(~~~) was ob6 3.33 (CMe), 1.35 (CCMe,), 1.14 (02CCMe3);I3C NMR 6 193.9 tained as dark red needles by recrystallization from ether a t -30 (02CCMe3),80.3 (CCMe,), 68.9 (CMe), 40.1 (CMe,), 33.5 (CMe,), "C (0.80 g, 82% of theoretical 0.98 g, three crops): 'H NMR 6 33.0 (CCMe,), 26.4 (O,CCMe,), 4.7 (CMe). 8.23 (HJ, 7.28 (H,), 7.04 (HJ, 3.54 (MeOCH2CH20Me),3.21 W[C3(CMe3)Etz](02CCMe3)3.3-Hexyne (51 pL, 0.45 mmol) (MeOCH,CH,OMe), 1.75 (CMe,); I3C NMR 6 252.9 (Cm),240.5 was added to a solution of W(CCMe3)(0,CCMe3)3(0.25 g, 0.45 (CJ), 234.8 (Co), 155.8 (4, J c F = 37 Hz, CF,CO2), 140.3 (Clpso), mmol) in pentane (10 mL). The color of the solution slowly 131.9 (Co),130.0 (C,), 128.9 (C,), 116.1 (9,JcF = 290 Hz, CF3C02), changed to deep red over a period of several hours. The solvent 72.0 (MeOCH2CH20Me),64.6 (MeOCH,CH,OMe), 46.3 (CMe,), was removed in vacuo to give a red oil that is essentially pure 31.4 (CMe,). Anal. Calcd for M o C ~ ~ H c, ~ 43.31; ~ ~ ~H,F 4.15. ~ : product: 'H NMR 6 4.19 (dq, 2, JHH = 15.1, 7.5 Hz, CFound: C, 42.83; H, 4.05. (CHAHBCH,)),3.74 (dq, 2, JHH = 15.1, 7.5 Hz, C(CH,HBCH,)), W[V~-C~(CM~~)E~,](O~CCF~)~. An excess of 3-hexyne (840 1.40 (CCMe,), 1.23 (t, CCH,Me), 1.15 (O2CCMe,); I3C NMR 6 fiL, 7.39 mmol) was added t o a solution of W194.0 (02CCMe3),81.5 (CCMe,), 74.3 (CEt), 40.1 (CMe,), 33.5 (CCMe3)(02CCF3),(dme)(1.00 g, 1.47 mmol) in ether (25 mL), (CCMe,), 31.3 (CMe,), 26.4 (02CCMe3),17.6 (CCH,Me), 15.2 and the solution was stirred overnight. A black crystalline powder (CCH,Me). precipitated from solution and was collected and dried in vacuo Mo[ C3(CMe3)(Ph)](02CCF3),(py),. Excess pyridine (175 pL, (0.27 g, 21%). The powder could be recrystallized from di2.15 mmol, 5 equiv) was added all at once to a dark red ether chloromethane at -30 "C to give large, black, paramagnetic (0.25 g, solution (15 mL) of MO[C~(CM~~)(P~)](O,CCF~)~(~~~) crystals. Anal. Calcd for WC25H&1208: C, 34.54; H, 3.36. Found: 0.429 mmol) a t -30 "C. The resulting solution darkened to C, 34.60; H, 3.39. ESR (CHZC12): g = 1.848. purple-red, and a purple powder precipitated. The mixture was W2(02CCMe3)6(3-hexyne).W,(OCMe& (2.00 g, 2.48 mmol) warmed to room temperature over the next 2 h, and solvents were was added to a solution of 6 equiv of pivalic acid (1.52 g, 14.9 removed in vacuo. The purple residue was recrystallized from mmol) in pentane (50 mL). The pentane was removed in vacuo a minimum amount of a 1:l mixture of ether and dichloromethane from the resulting yellow-brown solution. The residue was disa t -30 "C, yielding dark purple-red cubes (0.22 g, 78%, three solved in toluene (25 mL), and excess 3-hexyne (850 wL, 7.48 crops): 'H NMR 6 8.90 (H,-py), 8.71 (H,-py'), 8.17 (H,-Ph), 7.18 mmol) was added. The solution was placed in a Schlenk tube (H,-Ph), 6.95 (H,-Ph), 6.85 (H,-py and py'), 6.58 (H,-py), 6.53 and heated to 60 "C overnight to give a dark blue-green solution. (H,-py'), 1.70 (CMe,); I3C NMR (CD,C12) 6 251.0 (CCMe,), 245.7 The solvent was removed in vacuo to leave blue crystals that were (CPh), 231.5 (C&, 155.6 (q, JCF= 41 Hz, CF,C02), 150.8 (C,-py), essentially pure by 'H NMR. The product is highly soluble but 139.7 (C,-py), 139.4 (C,pqo-Ph), 133.7 (C,-Ph), 130.9 (C,-Ph), 129.0
c,
c,
Organometallics 1986, 5, 33-37 can be recrystallized from pentane a t -40 OC: 'H NMR (298 K) 6 5.0-4.6 (br, 4, CH3CHzC),1.48 (t,6, J = 7.3 Hz, CH&HzC), 1.23 (br s, 36, 02CCMe3),1.18 (s,18, OZCCMe3);'H NMR (360 K) 6 4.66 (q, 4, J = 7.3 Hz, CH,CH,C), 1.38 (t,6, J = 7.3 Hz, CH3CHzC), 1.24 (s, 36, 02CCMe3),1.21 (s,18, O2CCMe,);'H NMR (toluene-d8, 235 K) 6 4.91 (m, 2, CH~CHAHBC), 4.74 (m, 2, CH~CHACHBC), 1.71 (t, 6, J = 7.3 Hz, CH~CHACHBC), 1.24 (S, 18, OZCCMe3),1.21 (s, 18, 02CCMe,), 1.19 (9, 18, 02CCMe3);13C NMR (298 K) 6 217-213 (br, 02CCMe3), 203-200 (br, OZCCMe3), 193.9 (s, CH3CH2C),40.3 (s, OZCCMe3),39.5 (8,02CCMe3),30.7 (CH3CH2C),27.5 (02CCMe3),26.9 (OzCCMe3),16.1 (CH3CH2C). Anal. Calcd for W2C36H64O17: c, 40.92; H, 6.11. Found: c, 41.39; H, 6.15. Wz(02CCMe3)6(2-butyne).This compound was prepared in the same manner as the 3-hexyne derivative above as a blue, pure, highly crystalline solid in almost quantitative yield. It is extremely soluble in pentane and could not be recrystallized from pentane a t -40 OC: 'H NMR (toluene-d8, 360 K) 6 3.78 (s,6, CH3C), 1.22 (s, 54, 02CCMe3);'H NMR (300 K) 6 3.83 (br, 6, CH3C), 1.22 (s, 36, 0,CCMe3), 1.20 (s, 18, OZCCMe3);'H NMR (toluene-d8, 240 K) 6 3.91 (s,6, CH3C),1.24 (s, 18,02CCMe3),1.17 (s, 18, 02CCMe3), 1.10 (s, 18, OZCCMe3);13C NMR (CDZClz,225 K) 6 201.9, 196.5, 193.0, 190.8 (all singlets, OZCCMe3and CH,C); 40.3, 39.5, 38.8 (all singlets, 02CCMe3),26.9, 26.2, 26.0 (all quartets, 02CCMe3), 17.3 (CH3C). Wz(02CCH3),(3-hexyne). Excess acetic acid (700 pL, 12.2 "01) was added to a solution of w2(ocMe3)6(1.00 g, 1.24 mmol) in dichloromethane (10 mL). The red solution immediately turned yellow. The solvent was removed in vacuo to give a yellow powder. The powder was redissolved, and an excess of 2-butyne (425 wL, 3.74 "01) was added. The solution was heated to 60 "C overnight in a closed Schlenk tube. The solvent was removed in vacuo from the resulting solution. The product was extracted with minimal ether, and the extract was filtered through Celite in order to remove 2-butyne polymer. Cooling the filtrate to -40 "C gave dark blue prisms (0.55 g, 55%): 'H NMR 6 5.1-4.5 (br, 4, CH3CH2C),1.93 (br s, 12, OZCCH3),1.87 (s, 6, 02CCH3),1.45 (t, 6, J = 7.4 Hz, CH3CHzC);'H NMR (toluene-d, 235 K) 6 4.96 (m,
33
2, CH~CHACHBC), 4.67 (m, 2, CH~CHAHBC), 1.89 (br 9, 12, 0zCCH3), 1.78 (~,6,02CCH3),1.54 (t,6, J = 7.1 Hz, CH~CHAHBC); 13C NMR 6 233-230 (br, O2CCH3),198-194 (br, OZCCH3),188.0 (s,CH&HZC), 32.3 (CH&HZC), 24.0 (0zCCH3), 21.3 (OZCCHJ, 15.0 (CH3CHzC).Anal. Calcd for W2C18Hz801z:C, 26.88, H, 3.51. Found: C, 27.12; H, 3.67.
Acknowledgment. This work was supported by NSF G r a n t CHE84-02892 t o R.R.S. and in p a r t by NSF G r a n t CHESO-23448 to M.R.C. Registry No. W(CCMe3)(02CCMe3),, 99053-08-4; Mo(CCMe3)(0zCCMe3)3,99096-78-3; W(CCMe3)(02CCHMe2)3, 99053-09-5; M O ( C C M ~ ~ ) ( O ~ C C H M 99053-10-8; ~~)~, W(CCMe3)(O2CCH3),,99053-11-9; MO(CCM~~)(O,CCH,)~, 9905312-0; W ( CCMe,) ( 0 2 C C F 3 ) 3d( m e ) , 99053- 13-1; Mo(CCMe3)(O2CCF3),(dme), 99053-14-2; Mo[C3(CMe3)Mez](O2CCHMe2),,99096-79-4; Mo[C3(CMe3)Etz](OZCCHMez)3, 99053-15-3; MO[C,(CM~~)P~~](~~CCHM~,)~, 99053-16-4; Mo[C3(CMe3)MeZ](0,CCMe3),, 99053-17-5; Mo[C3(CMe3)Etz](0zCCMe3)3,99053-18-6; Mo[C3(CMe3)Ph2](02CCMe3)3, 99053-19-7; W[C3(CMe3)Mez](0zCCMe3)3, 99053-20-0; W[C3( C Me,) E t 2] ( OzCC Me3)3, 99053- 2 1- 1; M o [ C (C Me,) (Ph)l(OzCCFdz(~y)~, 99053-22-2; Mo[C3(CMe3)21 (O&CFJ2(dme), 99053-23-3; MO[C~(CM~,)~](O~CCF~)~(~~)~, 99053-24-4; W[C3(CMe3)Etz](O2CMe),, 99053-25-5; Mo[C3(CMe3)(Ph)] (OzCCF3)2(dme),99053-26-6; W [~5-C,(CMe3)Et,](02CCF3)4, 99053-27-7; W2(02CCMe3)6(B)(B = 3-hexyne), 99053-28-8; Wz(02CCMe3)6(B)(B = 2-butyne), 99096-80-7;W2(OZCCH3)&B) (B = 3-hexyne), 99053-29-9; W(CCMe3)Np3, 68490-69-7; Mo(CCMe3)Np3,68404-35-3;Wz(OCMe&, 57125-20-9;Me3CCOZH, 75-98-9; MezCHCO2H, 79-31-2; MeCOzH, 64-19-7; CF,COZH, 76-05-1; M e C e M e , 503-17-3;EtC=CEt, 928-49-4;PhCECPh, 501-65-5; Me3CC=CH, 917-92-0; PhCECH, 536-74-3.
,
Supplementary Material Available: A table of anisotropic thermal parameters (Table VS) and a listing of observed and calculated structure factor amplitudes (14 pages). Ordering information is given on any current masthead page.
Synthesis, Structural Characterization, and Regioselective Reactivity with Alkyl Iodides of the Rhodium Octaethy lporphyrin- Indium Octaethylpor phy rin Complex Nancy L. Jones, Patrick J. Carroll, and Bradford B. Wayland' Department of Chemistry, University of Pennsylvania, Philadelphia, Pennsylvania 19 104 Received April 29, 1985
T h e complex Rh(0EP)-In(0EP) (I) has been synthesized by t h e reaction of [Na][Rh(OEP)] with In(OEP)(Cl). T h e presence of a metal-metal bond in complex I was first suggested by interpretation of 'HNMR spectra and subsequently confirmed by a single-crystal X-ray diffraction study. T h e complex crystallizes in the monoclinic space grou Cih-C2/c with four molecules in a cell of dimensions a = 18.214 (3) A, b = 15.117 (3) A, c = 23.540 (3),!. @ = 106.92 (2)O, and V = 6201 A3. T h e final conventional and weighted agreement indices on F,, (F: > 3a(F:)) are R = 0.047 and R , = 0.055. T h e rhodium-indium metal-metal bond length is 2.584 (2) 8.The reactivity of I is consistent with the formulation of a polar covalent bond (Rh(I)-:+In(III)+) as manifested in t h e regioselective addition of alkyl iodides t o I.
Introd uction Heterobimetallic complexes in which the t w o adjacent metal fragments have differing properties have t h e potential for producing selective reactivity at each metal. The unusual organometallic chemistry of t h e r h o d i u m porphyrins'-* has p r o m p t e d u s t o initiate a program t o in(1) Wayland, B. B.; Woods, B. A. J. Chem. SOC.,Chem. Commun. 1981,700-701.
0276-7333/86/2306-0033$01.50f 0
corporate rhodium porphyrins i n t o metal-metal bonded heterobimetallic complexes. Initial studies of compounds containing rhodium octaethylporphyrin ( R h ( 0 E P ) ) with t r a n s i t i o n - m e t a l species ((0EP)Rh-M'; M' = Mo(2)Wayland, B.B.;Woods, B. A.; Minda, V. M. J. Chem. SOC.,Chem. Commun. 1982.634-635. (3)Wayland; B.B.;Woods, B. A.; Pierce, R. J. Am. Chem. SOC. 1982, 104, 302-303. (4)Setsune, J.-I.; Yoshida, Z.-I.; Ogoshi, H. J. Chem. SOC.,Perkin Trans. 1 1982,983-987.
0 1986 American Chemical Society
