Organometallics 1995, 14, 1911-1919
1911
Hybrid DiborolyVTricarbadecaboranyl Triple-Deckers: (q5-Cyclopentadieny1)cobalt - 20,. " I > 3.00.
5a
+
6
5b
C ~ B ~7Co HI 259.84 1210 (No. 15) 8
C~HI~B~N~ 235.59 P21/n 4
CxHpB7Ni 249.61 P21/n 4
C~B~HI~N~ 259.60 p2 1 2
14.4637(7) 7.948 l(7) 22.689(2) 94.027(4) 2601.9(3) 12.83 0.36 x 0.12 x 0.01 1.327 Mo ,?I (0.710 70) 2.0-25.0 f16,119.f26 I1429 3237 (Rmerse = 5.04) 1047" I54 0.046'
7.874( 1) I 1.984(2) 13.I89(2) 104.61( 1) 1204.4(3) 15.63 0.4 x 0.4 x 0.6 1.299 Mo K, (0.710 70) 2.33 -26.46 f9,114,f16 4249 2150 1763" 204 0.033' 0.083"
6.577(4) 15.104(IO) 13.395(9) 99.26(5) 13 13.3( 15) 14.38 0.3 x 0.5 x 0.8 1.262 Mo K, (0.710 70) 2.05-28.50 f8,+20,+17 3453 3323 2480' 219 0.035' 0.097d
8.6982(4) 10.0330(5) 8.0877(3) 117.017(2) 628.78(5) 15.05 0.22 x 0.22 x 0.10 1.371 Mo KO. (0.710 70) 2.0-25.0 fIO,& 1l , f 9 6075 1086 (Rmerre = 5.34) 1637b I54 0.030'
0.061'
0.042y
wR2 = [x[w(F,' - Fcz)z]/~~(Foz)z]l'?. 'Rz = ( x ~ ( I F o 1- IFcl)'/c~'lFol~)"'. R I = xllFoI - ~Fc~I/~IFoI.
-7.7 (lB), -9.6 (lB), -17.3 (lB), -19.7 (1B); MS (EI) m l z 507 [M+l, 313 [M+ - CH3C3B7HgNiI; HRMS calcd for 12C211H4011B959C055Ni 507.2707, found 507.2708; Anal. Calcd for C21H40BgCoNi: C, 49.69; H, 7.96. Found: C, 47.57; H, 8.03. Synthesis of 1-(tl5-CsHs)Co-(2-Me-2,3,5-C3B,H~) (4). A solution of Na+(6-Me-5,6,9-C3B~Hg)-(4.0 mL of a 0.36 M solution, 1.4 mmol) in THF was added dropwise while a solution of Na+CsHs- (0.7 mL of a 2.0 M solution, 1.4 mmol) (tls-C~H5)Co(p-~s-MeEt4C3Bz)Ni(t14-8-Me-7,8,10in THF was concurrently added dropwise to a stirred solution C&Hs) (3). Using a procedure similar to that for the of CoCl2 (0.18 g, 1.4 mmol) in THF, resulting in a color change synthesis of 1, a stirred mixture of Li+[(q5-C5H5)Co(q5from bright blue to dark green. After the mixture was stirred MeEt4C3Bz)I- (0.194 g, 0.61 mmol) and Na+(6-Me-5,6,9for 15 h a t room temperature, the solvent was vacuumC3B7Hg)- (0.102 g, 0.64 mmol) in THF (20 mL) was maintained evaporated. The oily green residue was dissolved in CHzCl2 at -80 "C, and a THF suspension of NiBr2.DME (0.225 g, 0.73 and filtered through a 2 cm plug of Florisil. The solvent was mmol) was added dropwise. The mixture was warmed to room vacuum-evaporated, and the dark residue was chromatotemperature and stirred for 14 h. Chromatography on alugraphed (Si02/4:1 hexane-CHzCl2) to give 0.260 g (0.78 mmol, mina with pentane-toluene (2:l) yielded, after crystallization 56%) of commo-Co-(l-C0-2-Me-2,3,5-C3B7Hg)2~~ and 0.122 g from pentane-CHzCl2 (10:l) at -30 "C, 0.62 g (1.22 mmol, (0.47 mmol, 34%) of dark red 4: mp 143 "C dec; paramagnetic; 20%) of pure 3: mp 178 "C; 'H NMR (CsD6,200 MHz) 6 3.93 HRMS calcd for 12C91H1711B759Co 261.1314, found 261.1326. (s, 5H, C5H51, 2.71 (s, 3H, CH3 of C3B2), 2.55-2.26 (m, 4H, Anal. Calcd for C ~ H ~ ~ B ~C,C41.60; O : H, 6.59. Found: C, CH2CH3), 2.40 (m, lH, CH-carb), 1.92-1.42 (m, 4H, CH2CH3), 40.66; H, 6.98. 1.55 (t, 3H, CH~CHS),1.29 (t, 3H, CH~CHS),1.14 (t, 3H, Synthesis of l-(p3-C3Hs)Ni-(rls-2-Me-2,3,5-C3B,H~) (Sa). CH~CHS), 0.94 (s, 3H, CH3-carb), 0.75 (t, 3H, C H Z C H ~ llB );~~ A solution of Naf(6-Me-5,6,9-C3B7H9)- (0.122 g , 0.77 mmol) NMR (C6D6, 64.2 MHz) d 14.1 (2B),9.7 (lB), 5.3 (lB),2.0 (lB), in THF (10 mL) was maintained at 0 "C, while a THF solution of [(HC(CH2)2)NiBr12(0.18 g, 0.49 mmol) was added dropwise. (22) One CH hydrogen was not found in the 'H NMR for 3 but is The solution was stirred for 3 h at room temperature and then suspected to be obscured by the four triplet systems.
suspension of CoCl2 (0.055 g, 0.42 mmol) was added dropwise. After removal of the solvent, the product was isolated by chromatography on alumina with hexane-CHzC12 (3:l) to yield 0.63 g of crude 2. Recrystallization from pentane-CHzCl2 (10: 1) gave 0.48 g (0.95 mmol, 27%) of pure 2: mp 158 "C; paramagnetic; MS (EI) m l z 508 [M+], 313 [M+ - MeC3B7HgCo]; HRMS calcd for 12Cz11H&B959Co508.2682, found 508.2686.
1918 Organometallics, Vol. 14, No. 4, 1995
Weinmann et al.
Table 4. Refined Positional Parameters for atom
X
v
z
c oI Fe 1 c2 c3 c5 C5m C13 C15 C16 C17 C18 C19 c20 c 2I c22 C23 C24 C25 C26 C27 C28 C29 C30 B4 B6 B7 B8 B9 B 10 B11 B12 B14
-0.045 13(9) -0.00289(9) -0.1097(8) 0.1394(7) -0.0289(7) -0.0625(9) -0.0447(7) 0.0492(8) -0.0702(7) -0.2643(7) -0.339 l(8) -0.0625(9) 0.1826(8) 0.2875(8) 0.1323(7) 0.1461(9) -0.1204(8) -0.1762(8) -0.151(1) -0.054( I ) 0.032( I ) -0.0 15( 1) -0.129( 1) -0.0745(9) 0.106( 1) 0.069( I ) -0.083( I ) 0.146( I ) 0.022( I ) 0.048( 1) -0.1358(8) 0.07 17(8)
0.58786( 8) 0.4271 l(8) 0.3359(6) 0.3963(6) 0.2633(6) 0.1818(6) 0.5689(6) 0.4692(5) 0.4471(5) 0.5005(7) 0.576( 1) 0.64 18(6) 0.6046(6) 0.59 I ( 1) 0.4148(7) 0.4465(7) 0.3690(5) 0.4039(7) 0.65 1x8) 0.63 1 l(7) 0.6774(8) 0.7272(6) 0.7106(7) 0.4002(9) 0.2944(8) 0.4336(9) 0.2755(9) 0.32% I ) 0.33 15(8) 0.2366(9) 0.5077(6) 0.5492(6)
I. 1 I975(7) 0.96834(7) 0.91 88(7) 0.9130(6) 0.937 I(6) 0.9987(7) 0.9817(5) 1.0957(5) 1.0972(5) I .OO22(7) 1.0278(9) 0.9082(6) 0.9979(7) 1.0495(8) 1.1531 0 ) 1.2516(6) 1.1557(6) 1.2420(6) 1.2 101(9) 1.2531(7) 1.2085(9) I . 1364(8) 1.1388(8) 0.8343(8) 0.9439(8) 0.8298(8) 0.8240(9) 0.826( I ) 0.7696(7) 0.845 I ( 8) I .0256(7) 1.0239(6)
+
+
+
Table 6. Refined Positional Parameters for Beq."
atom
X
v
z
3.01(5) 2.39(4) 3.8(4) 3.7(4) 3.6(4) 5.6(4) 2.9(4) 2.8(4) 2.34) 4.6(4) 9.0(4) 4.8(4) 5.0(4) 8.7(4) 3.7(4) 5.6(4) 3.3(4) 4.8(4) 5.9(4) 6.3(4) 5.8(4) 5.3(4) 5.1(4) 4.0(4) 3.7(4) 4.1(4) 434) 5.3(4) 4.8(4) 4.7(4) 2.7(4) 2.8(4)
Ni9 c o1 c7 C8m C8 c10 C13 C15 C16 C17 C18 C19 c20 c 21 c22 C23 C24 C25 C26 c27 C28 C29 C30 BI B2 B3 B4 B5 B6 B11 B12 B14
0.2556 l(2) 0.25783(3) 0.1426(2) 0.2581(3) 0.2478(2) 0.1690(2) 0.1855(2) 0.3726(2) 0.2766(2) 0.0227(3) -0.0814(3) 0.1038(3) 0.4004(3) 0.4593(4) 0.5014(3) 0.5726(3) 0.2930(4) 0.2495(5) 0.3516(3) 0.2566(3) 0.15 15(3) 0.18 13(4) 0.3060( 3) 0.3 171(3) 0.1675(3) 0.2763(3) 0.3562(2) 0.3063(3) 0.1931(3) 0.0869(3) 0.1485(2) 0.3256(2)
0.18412(2) 0.34458( 2) 0.0183(2) --0.0145(2) 0.0409(2) 0.1947(2) 0.2182(2) 0.2876(2) 0.3284(2) 0.3295(2) 0.2656(3) 0.1648(2) 0.1409(2) 0. I79 l(3) 0.3 170(3) 0.2683(3) 0.4000(2) 0.4953(3) 0.41 16(2) 0.3629(3) 0.3969(3) 0.4664(3) 0.4764(2) 0.06 18(2) 0.0168(2) --0.02 14(2) 0.0785(2) 0.1759(2) 0.1290(3) 0.107 1(2) 0.2904(2) 0.2086(2)
0.02632(2) -0.1277 l(2) 0.078 l(2) -0.0503(2) 0.03 16(2) 0.13 14(2) -0.105(1) -0.0336(2) 0.0053(2) -0.0220( 2) -0.0375(3) -0.17 I8(2) -0.1532(2) -0.227 l(3) -0.0152(2) 0.0578(2) 0.0773(2) 0.0569(3) -0.2152(2) -0.2584(2) -0.2320(2) -0.17 18(2) -0.1606(2) 0.2056(2) 0.1885(2) 0.1252(2) 0.0970(2) 0.1638(2) 0.2217(2) 0.1280(2) -0.040 l(2) -0.0993(2)
('Be, = X/3[Ull(aa*)? Ul?(hh*)? U ~ J ( C C * ) ?2U~2aa*hh*(cosy ) 2U13aa*cc*(co.sp) 2U23hh*cc*(cos a)].
+
+
B,,."
w2
3.27( I ) 3.66(2) 4.26(4) 5.07(4) 3.91(4) 4.17(4) 3.55(4) 3.86(4) 3.81(4) 5.37(4) 8.52(4) 5.12(4) 5.36(4) 7.16(4) 5.83(4) 7.05(4) 5.99(4) 8.74(4) 5.44(4) 5.60(4) 5.93(4) 6.31(4) 5.82(4) 4.68(4) 4.86(4) 4.60(4) 4.07(4) 4.19(4) 4.76(4) 4.56(4) 3.73(4) 3.7 l(4)
