Stepwise Approach to Metal-Capped 4-Fold-Bridged

Synthesis and Properties of a Superphane with One Thiophene and One CpCo-Stabilized Cyclobutadiene Ring. Silke Gath, Rolf Gleiter, Rolf J. Schaller, a...
0 downloads 0 Views 1MB Size
Download PDF
975

Organometallics 1995, 14, 975-986

Stepwise Approach to Metal-Capped 4-Fold-Bridged Cyclobutadienophanes Rolf Gleiter,"??Heinrich Langer,? Volker Schehlmann,? and Bernhard N u b e r t Organisch- und Anorganisch-Chemisches Institut der Universitat Heidelberg, 0-69120 Heidelberg, Germany Received September 30, 1994@

The three cyclic alkynes 5-cyclononynol (31),5-cyclodecynol (151,and 6-cycloundecynol (16)are dimerized with CpCo(C0D) to the tricyclic dialcohols 17,24,and 32,respectively. Oxidation of t h e alcohols yields the diketones 18,19,25,and 33 which can be transformed to the tricyclic diynes 23, 29, 30, and 36 via the bis(selenadiazo1e)s. Reaction of 23 with CpCo(CO)2, C ~ * C O ( C O and ) ~ , Fe(C0)5 yields superphanes i n which both complexed cyclobutadiene (Cb) units are connected with four trimethylene chains. The reaction of 29/30 with CpCo(CO)2 affords two isomeric CpCo-stabilized fourfold-bridged bicyclo[4.2.0locta2,4,7-dienes 43 and 44 besides the expected superphane 42 in which the CpCo-capped Cb units are connected by two trimethylene and two tetramethylene chains. The key compounds, tricyclic diynes 23 and 36,superphane 40,and bicyclooctatriene 44,have been characterized using X-ray structural analysis. Crystal data: 23, C25H29C~,triclinic, space group Cli, Pi (NO.2),a = 9.003A, b = 10.399 c = 11.874 A, a = 93.45",p = 101.45",y = 108.77", V = 1022.34Hi3, 2 = 2;36,C23H25C0 rhombic, space group D42,P212121 (No. 19),a = 9.555(9) b = 12.86(1)A, c = 15.551(9) V = 1910.9 A3, 2 = 4;40,C28H29CoFe03, monoclinic, Cc (No. 9),a = 18.92(1) b = 8.499(6) c = 19.37(1)A, /3 = 130.16",V = space group C4s, 2380.41A3, 2 = 4;44,C27H33C~, triclinic, space group Cli,Pi (No. 2),a = 8.269(3)A, b = 9.082(2) c = 13.72.4A, a = 84.87(2)",p = 88.77(3)",y = 80.62(2)",V = 1012.8A3, 2 = 2.

A,

A,

A,

A,

A,

A,

Introduction In superphanes two n-units are connected with each other by the maximum number of chains.l If the n-units are conjugated ring systems such as benzene,2 thioor cyclo~ h e n e or , ~metal-stabilized ~yclopentadienyl~ butadiene, this leads t o rigid cages which are excellent model compounds to study all kinds of interaction between the n-units. For these studies it is desirable to have a simple synthesis of superphanes which allows the variation of the length of the spacer chains. Recently we showed that 1,6-cyclodecadiyne (1)reacts with (q5-cyclopentadienyl)dicarbonylcobalt [CpCo(C0)~1t o yield the superphane 2 (Scheme l).516 So far this reaction could be extended on the one hand to cobalt reagents with functionalities in the Cp ring7,8and on the other hand to 4,9-diisopropylidene-1,6-cyclodecad i ~ n e ' ,as ~ well as 1,8-cyclotetradecadiyne7Jo and 1 , l O cyclooctadecadiyne. Organisch-Chemisches Institut.

* Anorganisch-Chemisches Institut. +

@Abstractpublished in Advance ACS Abstracts, January 1, 1995. (1)The attribute super was suggested by Prof. H. Hopf for the first 6-fold-bridged cyclophane, [2~](1,2,3,4,5,6)cy~lophane.~ (2)Sekine, Y.; Brown, M.; Boekelheide, V. J.Am. Chem. SOC.1979, 101,3126. (3)Takeshita, M.; Koike, M.; Tsuzuki, H.; Tashiro, M. J.Org. Chem. 1992,57,4654. (4)Hisatome, M.: Watanabe, J.: Yamakawa, IC; Iitaka, Y. J.Am. Chem. SOC.1986,108,1333. (5)Gleiter, R.;Karcher, M.; Ziegler, M. L.; Nuber, B. Tetrahedron Lett. 1987,28,195. (6) Gleiter, R.; Kratz, D. Tetrahedron Lett. 1990,31,5893. (7)Reviews: Gleiter, R.Angew. Chem., Znt. Ed. Engl. 1992,31;27. Gleiter, R.; Kratz, D. ACC.Chem. Res. 1993,26,311. ( 8 )Gleiter, R.;Pflasterer, G. Organometallics 1993,12,1886. (9)Gleiter, R.;Merger, R.; Nuber, B. J.Am. Chem. SOC.1992,114, 8921.

(T)-

Scheme 1"

a

1 _y_ P^

U

3

4

Key: (a) C~CO(CO)Z.

Scheme 2

P

0,- .Wp 5

6

7

M'

8

Superphanes with different chain lengths in one molecule or those which are capped by different metal (10)Gleiter, R.; Treptow, B.; Kratz, D.; Nuber, B. Tetrahedron Lett. 1992,33,1733. (11)Gleiter, R.; Masterer, G.; Nuber, B. Chem. Commun. 1993,454.

0276-733319512314-0975$09.0010 0 1995 American Chemical Society

976 Organometallics, Vol. 14, No. 2, 1995

Gleiter et al.

Scheme '3

n=3 n=4

9 10

n=3 n-4

Figure 1. Comparison between the conformations of 18 as determined by X-ray investigations and of 1,6-cyclodecadiene (left). Although our efforts to prepare monoprotected cyclic diacetylenes were successful with Co2(CO)s and CH3Re021,12 we were not able so far to obtain protected tricyclic diynes such as 6. In this paper we report an alternative approach in which a masked cyclic diyne is used as building b10ck.l~ [341(1.2.3.4)- and [4~3~1(1.2.3.4)Cyclobutadienophanes. Starting materials for our synthesis are 5-cyclodecynol ( 15)14and 6-cycloundecynol (16).15The preparation of 15 and 16 (Scheme 3) uses the Eschenmoser-Tanabe fragmentation16 as the key step. According to the protocol shown in Scheme 3 both starting materials can be prepared easily in gram quantities.

16

14 (I

11 12

Key: (a) HzOdOH-; (b) TosNHNH2, A; (c) LiAlH4.

fragments are not available in the one-pot route indicated in Scheme 1. To enhance the synthetic potential for the preparation of metal-stabilized superphanes, a stepwise procedure is desirable. In principle this could be achieved by starting with a monoprotected cyclic diacetylene such as 5 (Scheme 2). After dimerization and removal of the protecting group at the triple bonds, a second metal fragment M could be used to form the second cyclobutadiene unit.7 This sequence should allow the preparation of cyclobutadienophanes of variable chain length and with different metals.

~~

(12)Gleiter. R.: Schehlmann. V.: Kohler. M. UnDublished results. (13)Preliminary publication:' Gleiter, R:; Schehimann, V. Angew. Chem., Znt. Ed. Engl. 1990,29,1426. (14)Hanack, M.;Harding, C. E.; Derocque, D. C. Chem. Ber. 1972, 105, 421. (15)Gleiter, R.;Langer, H.; Wittwer, W. Manuscript in preparation.

Scheme 4~ CP I co

I D O H 15

CP I

- m"" CO

a

+

HO

17a

17b

I

I

co

b

18

-

19 CP I co

C

NH2CONHN

NNHCONH?

20 CP

21

22

Metal - Capped Cyclob utadienopha nes

Organometallics, Vol. 14, No. 2, 1995 977

Scheme 5”

27

e

28

m+w 29

a

30

Key: (a) CpCoCOD; (b) Oppenauer oxidation; (c) semicarbazide acetate; (d) SeOflOAc; (e) n-BuLmHF,

Scheme 6” CP

co

32

31 co

33

36 a

Key: (a) CpCoCOD; (b) Oppenauer oxidation; (c) semicarbazide acetate; (d) SeOflOAc; (e) n-BuLmHF.

The reaction sequence for the further steps is shown in Schemes 4 and 5. Heating a very dilute solution of 15 in decalin with CpCo(C0D) yields the tricyclic alcohols 17. Due to the symmetry of 15, two regioisomers (17a,b) are expected. From each of the two regioisomers three stereoisomers can be anticipated. In (16) Schreiber, J.;Felix, D.; Eschenmoser, A.; Winter, M.; Gautschi, F.; Schulte-Eke, K. H.; Sundt, E.; Ohloff, G.; Kalvoda, J.; Kaufmann, H.; Wieland, P.; Anner, G. Helu. Chim. Acta 1967,50,2101.

the case of 16 the regiochemistry is unambiguous and three stereoisomers are expected. The yields obtained in this dimerization step are moderate (40% for 17)to good (71% for 24). The mixture of the alcohols is oxidized using the Oppenauer procedure. In the case of 17 a 1:l mixture of the two regioisomeric ketones 18 and 19 is obtained with an overall yield of 83%. The two ketones have been separated for their characterization with silica gel using CHzClz as eluent, but

Gleiter et al.

978 Organometallics, Vol.14,No. 2, 1995 Scheme 7"

4

2

4

23

39

41

0

0 a

Key: (a) CpCo(CO)2; (b) CpCo(COh,MeCOz-=-C02Me;

40

(c) Cp*Co(C0)2; (d) Fe(CO)s.

Scheme 8"

B

c

A

d, A (relative energy, kcal mol): 3.9 (10.0);6.3 (0.0);4.6 (8.3). a

Scheme W

29/30

a

m

+

Figure 2. ORTEP drawing of 23 (50% probability ellipsoids). Key: (a) CpCo(C0)dc-octane.

normally the mixture is used for further reactions. With the same procedure 25 is obtained in 83% yield. The bis(selenadiazo1e)s of the diketones can be obtained by

reacting them with semicarbazide acetate and subsequent heating with SeO2. With this strategy we obtained two bis(selenadiazo1e)s in each case, 21 and 22 for the C20 system and 27 and 28 for the C22 system. The mixture was used for the subsequent step. Treatment of the respective mixtures with n-butyllithium

Metal-Capped Cyclobutadienophanes

Organometallics, Vol. 14, No. 2, 1995 979 Scheme 1W

Scheme 11"

'@ 36

c13

25

a

01

Figure 3. Structure of 40 as determined by X-ray investigations: View along the Fe-Co axis (lefi); side view (right, 50% probability ellipsoids).

(BuLi) in tetrahydrofuran at -40 "C yields exclusively 23 (71%) in the case of 21/22.Reaction of 27/28affords the anticipated mixture of two diynes, a 1 : l ratio of 29 and 30. Scheme 6 shows that starting from 5-cyclononynol (31)17a further tricylic diyne can be built up in a way similar to the described synthesis of 23 and (17)Lange, G. L.; Hall, T. W. J. Org. Chem. 1974,39, 3819.

C20

M = Cp*Co, MeCpCo, and CpCo.

29/30.18Since the second selenadiazol unit in 35 is formed regioselectively, only one of the two anticipated diynes (36)is obtained. X-ray investigations on single crystals of 36 show that the isomer with CZsymmetry is formed (Figure 6). Before describing our further steps, it is worthwhile to comment on the regioselectivity observed in the formation of only two bis(selenadiazo1e)s from 18 and 19 although four regioisomers are possible. To rationalize this fact we consider in Figure 1 the conformation of 18.19 The conformation of the 10-membered rings shows a great similarity with the lowest energy confor(18) 33 can be also prepared directly starting from 5-cyclononynone: Gleiter, R.; Schehlmann, V. Tetrahedron Lett. 1989,30, 2893. Nevertheless the better overall yield is obtained starting from 31. (19) X-ray structure analysis: Gleiter, R.; Schehlmann, V.; Nuber, B. Unpublished results.

c21 W

Figure 4. Structure of 44 as determined by X-ray investigations: View onto the cyclobutene unit (left, 50%probability ellipsoids); side view (right, full circles represent the butadiene unit).

980 Organometallics, Vol. 14, No. 2, 2995

Gleiter et al.

Table 1. Crystal Data and Data Collection Parameters 36

23 mol formula fw cryst syst space group cell dimens a, 8,

b,

8.

c, A

a, 8,

A 8,

Y,8,

v,A3

Cz5HzgC0 388.44 triclinic C'j, P1 (NO. 2)

CZ~HZ~CO 360.38 rhombic 0 4 2 , EL12121 (NO. 19)

C~8H~gCoFe03 528.32 monoclinic C4,, Cc (No. 9)

Cz7H33C0 416.45 tricIi@c C'i, P1 (NO. 2)

9.003 10.399 11.874 93.45 101.45 108.77 1022.34

9.555(9) 12.86(1) 15.551(9)

18.92(1) 8.499(6) 19.37(1)

8.269(3) 9.082(2) 13.724(5) 84.87(2) 88.77(3) 80.62(2) 1012.8 2 296 1.37 8.6 444 A(Mo Ka) = 0.710 73 w h, 0-12; k, -13 to 13; I, -19 to 19 3.0-57.5 5623 empirical, 7 rflns 0.87 < 20 < LOO 3916, I > 2.5u(I) 255 0.042 0.038 2.22 0.55/-0.53

Z

n

T, K

296 1.26 8.4 412 I(Mo Ka) = 0.710 73 w h, 0-13; k, -15 to 15; 1, -17 to 17 3.0-57.5 5344 empirical, 6 rflns 0.92 < 20 < 1.00 3891, I > 2.5u(I) 236 0.042 0.040 2.8 0.30/-0.47

dCdc.g - ~ m - ~ linear abs, p, cm-I

F(0OO) radiation, A scan type rflns measd 20 range, deg no. of r f l n s measd abs cor range of transmissn no. of unique obsd data no. of params (NV) R(F)

RdF) GOF

e, residual, e8,-3(mdmin)

44

40

L

130.16 1910.3 4 296 1.25 8.9 760 I(Mo Ka) = 0.710 73 w h, 0-11; k, 0-15; I, -18 to 18 3.0-44.0 2792 empirical, 6 rflns 0.91 < 20 < 1.00 1303, I > 2.5u(I) 218 0.063 0.046 1.71 0.651-0.49

2380.41 4 296 1.47 13.3 1096

I ( M o Ka) = 0.710 73 elm h, 0-27; k, 0-12; I , -27 to 27 3.0-60.0 3691 empirical, 5 rflns 0.67 < 20 < 1.00 1905, I > 2.5u(I) 297 0.045 0.035 2.10 0.501-0.38 c5

Figure 6. Calculated (AM11 geometries of the Cz2H28 fragments of 29 (left)and 30 (right). Full circles represent the sp centers. mation of 1,6-cyclodecadiene(left). Other isomers like 37 and 38 are derived from the 1,5-cyclodecadiene skeleton. Since 1,5-cyclodecadiene is by 7.0 kcallmol

Ct

(AM1 calculation) less stable than 1,8cyclodecadiene, it seems reasonable that the already performed 1,6cyclodecadiene conformation is maintained throughout the reaction, thus leading to 21 and 22 only. Preparation of the Superphanes. [341(1.2.3.4)Cyclobutadienophanes. The reaction of 23 with CpCo(C0)n in cyclooctane (120 "C) yields in only 2 h the superphane 2 (80%yield) and in traces (1%yield) the mixed phane 4. The reaction with (q5-pentamethylcyclopentadieny1)cobalt dicarbonyl [Cp*Co(CO)21in decalin yields 39 in 80% yield. Heating 23 with Fe(C0)5 in refluxing toluene leads to 40 in 8%yield. Finally, when heating 23 in the presence of dimethyl acetylenedicarboxylate (DMAD) and CpCo(C0)ain toluene yields the mixed cyclophane 41 as minor product besides 2 (Scheme 7). The quick reaction of 23 with CpCo(C0)n supports our assumption that 23 is an intermediate in the formation

Figure 6. ORTEP drawing of 36 (50% probability ellipsoids). of 2 from 1 (Scheme 1). The structure of 23,obtained from an X-ray investigation (Figure 2), shows that the two triple bonds are situated in the same half space and orientated parallel to each other. Calculations using the AM1 method on a model of 23 which does not contain the CpCo unit but allows the minimization of all geometrical parameters are in agreement with the X-ray data. These calculations predict besides the global minimum A, in which both triple bonds are 6.3 A apart, two local minima, B and C, in which the triple bonds are 3.9 and 4.6 A apart. The local minima are predicted to be 10.0 and 8.3 kcallmol higher in energy than A. These results explain the fast reaction of 23 with CpCo(Cola at higher temperature and the good yield.

Organometallics, Vol. 14, No. 2, 1995 981

Metal-Capped Cyclobutadienophanes Table 2. Atomic Coordinates ( x 104) and Equivalent Isotropic Displacement Parameters x 103) for CDHzgCo (23)

(Az

atom

co

c1 c2 c3 c4

c5

C6 c7 C8 c9 c10 c11 c12 C13 C14 c15 C16 C17 C18 C19 c20 c21 c22 C23 C24 C25

X

1694(1) -280(3) -350(3) -364(3) -292(3) -287(3) -1911(4) -2843(3) -3 155(4) -3259(4) -3 174(4) -2258(3) -556(3) -486(3) -2188(4) -3015(4) -3058(4) -2998(4) -2802(4) - 199l(3) -326(3) 3736(3) 371t(3) 3697(3) 3710(3) 3730(3)

Y

z

2853(1) 2534(3) 1337(2) 2104(3) 3301(3) 4720(3) 4942(3) 4969(3) 3717(4) 2743(4) 1534(4) 813(3) 1728(3) - 117(3) - 1182(3) - 1751(3) -651(4) 296(4) 1572(4) 2804(3) 2867(3) 3106(3) 2262(3) 2983(3) 4284(3) 4382(3)

2646(1) 322l(2) 2476(2) 1492(2) 2236(2) 2098(3) 2058(3) 842(3) W3) -517(3) -1189(3) -439(2) 210(2) 2604(2) 2157(3) 3100(3) 3911(3) 4509(3) 5209(3) 4647(3) 4455(2) 3896(3) 2941(3) 2002(3) 2359(3) 3550(3)

ueqa

"Equivalent isotropic U defined as one-third of the trace of the orthogonalized U, tensor.

The X-ray investigation on single crystals of 40 reveal a very similar skeleton as for 2. The distance between the two cyclobutadiene units amounts t o 2.98 A. Just as in 2 the four propano chains show a pinwheel conformation. [42321(1.2.3.4)Cyclobutadienophanes. The reaction of the mixture of 29/30with CpCo(CO)2yields the superphane 42 and the bridged bicyclo[4.2.0locta-2,4,7triene complexes 43 and 44 in a 2:l:l ratio.20 The unexpected formation of 43 and 44 is accounted by a [4 21 cycloaddition between a cobaltole and a CpCocyclobutadiene unit.21 Figure 4 shows two views of the structure of 44 obtained from an X-ray investigation. 42 is the first cyclobutadienosuperphane in which the two cyclobutadiene units are connected by chains of different length. An X-ray investigation on single crystals of 42 confirms the predicted structure.21 Obviously only 29 reacts to form a cyclophane. Using the AM1 procedure to calculate the geometrical parameters of the C22H28 fragment of 29 and 30 resulted in the conformations of minimum energy shown in Figure 5. We notice that in 29 the two triple bonds are orientated parallel to each other while in 30 the triple bonds are inclined by 8.6". The result that only 29 reacts t o form a superphane is reminiscent of the outcome of the reaction of 175-cyclodecadiyne(45)with CpCo(C0)z in n-octane.16 It has been found that only one of the possible dimerization products, 46,reacts to form a cyclophane (481,while the other (47)resists further ring closure with CpCo(CO12.

+

(20) Unbridged Fe(CO)&abilized bicyclo[4.2.0locta-2,4,7-trienes: Cooke, M.; Howard, J. A. K.; Rum, C. R.; Stone, F.G . A.; Woodward, P. J. Organomet. Chem. 1974, 78, C43. Slegeir, W.; Case, R.; McKennis, J. S.; Pettit, R. J.Am. Chem. SOC. 1974, 96, 281. (21) Preliminary publication: Gleiter, R.; Langer, H.; Nuber, B. Angew. Chem., Int. Ed. Engl. 1994,33, 1272. (22) Gleiter,R.; Kratz, D.; Ziegler, M. L.;Nuber, B.Tetrahedron Lett. 1990,31,6175.

Table 3. Atomic Coordinates ( x 104) and Equivalent Isotropic Displacement Parameters x 103) for CznH~9CoFe03(40)

(A2

atom Fe

c1 01

c2 02 c3 03 co c4

c5 C6 c7 C8 c10 c11 c12 C13 C14 C15 C16 C17 C18 C19 c20 c21 c22 C23 C24 C25 C26 C27 C28 C29

X

4008(1) 3508(6) 3174(5) 4924(7) 5551(5) 3234(7) 2711(4) 5000

4881( 14) 4478(89) 5 131( 14) 5909(13) 5799(14) 3769(6) 3799(8) 4761(8) 4760(7) 4263(8) 4271(7) 5253(7) 5250(7) 3100(7) 2793(7) 3520(7) 3113(6) 3403(7) 3540(7) 5522(7) 6265(8) 5962(7) 5492(6) 5608(6) 5911(6)

Y

4438(1) 6359(10) 7567(7) 4718( 10) 4869(8) 3626( 11) 3054(7) 883(1) - 1 163(13) -20(18) 1034(14) 598(25) -725(26) 2629(8) 4140(9) 4320(8) 2814(9) 974(10) 2475(9) 2655(9) 1146(10) 1298(10) 554(11) -145(11) 498l(9) 5087( 11) 3581(11) 5392( 10) 4672( 11) 3934( 10) 1722(9) 147(9) 248(9)

Z

7220(1) 6910(6) 6662(5) 8401(7) 9174(4) 7337(6) 7404(4) 5000 4424(12) 3809(7) 4069( 11) 4810( 15) 5041(10) 638l(6) 6063(7) 6820(7) 715l(6) 5393(7) 5043(6) 5806(6) 6164(6) 602l(6) 5163(7) 5152(7) 5155(6) 4587(7) 4278(6) 7047(7) 7076(8) 6180(7) 7893(5) 7593(6) 7022(6)

=Equivalent isotropic U defined as one-third of the trace of the orthogonalized Uo tensor.

Table 4. Atomic Coordinates ( x lo4) and Equivalent Isotropic Displacement Parameters (A2x 103) for CuHxCo (36) atom

co

c1 c2 c3 c4 c5 C6 c7 C8 c9 c10 c11 c12 C13 C14 C15 C16 C17 C19 c20 c21 c22 C23

X

8611(2) 9322(30) 10255(28) 10664(15) 979l(28) 8971(22) 6934(12) 6757(11) 7793(11) 7968(11) 5826(12) 4294(13) 4046(13) 5025(19) 6021(16) 7393(13) 8397(11) 8771( 12) 7142(15) 603319) 5453(20) 4907(13) 6173(11)

Y

9361(1) 8036(18) 8775(18) 8986(15) 8405(19) 7853(15) 9907(9) 9811(9) 10610(11) 10697(10) 9153( 9) 9537(11) 1024310) 11 139(15) 11600(15) 12098(10) 11216(9) 12543(9) 12618(11) 11807(11) 11063(11) 10038( 10) 9420(8)

Z

uwa

622( 1) 1266( 14) 1174(13) 402(17) -135(9) 423(17) 70(6) 1002(6) 1128(5) 214(6) 1563(6) 1659(7) 2454(8) 248(11) 2412(10) 2178(7) 1877(6) -451(7) - 1212(8) - 1249(8) - 1230(9) -99 l(7) -680(6)

"Equivalent isotropic U defined as one-third of the trace of the orthogonalized Uij tensor.

In 46 both acetylene units are orientated parallel to each other, while the 47 the triple bonds cannot be aligned parallel t o each other. Thus it was not unexpected that all attempts t o generate a cyclobutadienosuperphane like 49 starting from 36 failed (Scheme 111, although the distance between the triple bonds is not

Gleiter et al.

982 Organometallics, Vol. 14, No. 2, 1995

Table 5. Atomic Coordinates ( ~ 1 0 4 and ) Equivalent the mechanism of the superphane formation and the Isotropic Displacement Parameters (Azx 103) for C Z ~ H ~ J C O reactivity of CpCo-complexed cyclobutadienes.

(44)

atom

X

Y

Z

co c1 c2 c3 c4 c5 C6 c7 C8 c9 c10 c11 c12 C13 C14 C15 C16 C17 C18 C19 c20 c 21 c22 C23 C24 C25 C26 C27

2330(1) 2249i4j 3475(4) 4595(4) 4045(4) 2604(4) 292(3) 640(3) 2207(3) 2448(3) 805(3) 516(3) 2151(3) 1649(3) 1574(3) 3047(4) 3210(4) 346 l(3) - 1393(3) -2151(3) - 1030(3) -279(3) -643(4) -1598(3) -581(3) 4004(3) 3887(4) 3 15l(3)

3100(11 4262i4j 2993(4) 3159(4) 4506(4) 5178(3) 3079(3) 1802(3) 921(3) 471(3) 137(3) 1411(3) 1909(3) 3278(3) 4772(3) 482 l(3) 3576(3) 2068(3) 3934(3) 3108(3) 2394(3) -969(3) -1136(3) 223(3) 1327(3) -686(3) -1547(3) -363(3)

1466(1) 69&j 111(2) 1234(2) 1234(2) 767(2) 2265(2) 711(2) 1946(2) 3045(2) 3502(2) 3946(2) 3604(2) 2870(2) 3315(2) 3935(2) 4753(2) 4336(2) 2447(2) 3374(2) 4246(2) 3288(2) 2208(2) 1600(2) 055(2) 3104(2) 2211(2) 1405(2)

u,*

See footnote a of Table 4.

Table 6. Selected Interatomic Distances (A) and Angles (deg) for Compounds 23,36,40, and 44 Compound 23 co-Cl c 1-c2 C8-C9

1.966(3) 1.460(4) 1.160(5)

Co-C21 C3-C4 C8-Cl7

2.052(3) 1.459(4) 6.3

C8-C9-C10

172.7(4)

C15-Cl6-Cl7

174.1(4)

co-Cl C6-C7 C13-Cl4

Compound 36 2.090(23) Co-C6 1.464(14) C7-C8 1.122(25) C13-C21

1.949(11) 1.441(17) 5.7

C12-Cl3-Cl4 c19-c2o-c21

160.9(20) 164.3(18)

167.3(17) 164.4(16)

cO-c4 Fe-C1 ClO-c11 ClO-Cl4

C13-CI4-Cl5 C2O-C21-C22

Compound 40 1.999(16) Co-C14 1.786(9) Fe-C10 1.451(14) C14-Cl5 2.98

1.974(18) 2.064(10) 1.449(14)

co-c1 co-C8 C7-C8 c10-Cll

Compound 44 2.101(3) Co-C6 2.047(2) C6-C7 1.435(3) C9-C10 1.341(3) Cll-C12

1.992(2) 1.430(3) 1.547(4) 1.544(4)

C6-C7-C8 C8-C9-C10

112.2(2) 109.0(2)

113.6(2) 104.6(2)

C7-C8-C9 Cll-Cl2-Cl3

as far as in 23. The structure obtained of X-ray investigations (Figure 6) shows that the triple bonds are inclined by 28".

Conclusions Starting from cyclic alkynols, which can be looked at as masked cyclic diynes, we could develop a straightforward synthesis of cyclobutadiene superphanes which are capped with different metal fragments. The chain length depends on the starting cyclic alkynols. Our studies provided us also with new insights concerning

Experimental Section Equipment. All melting points are uncorrected. The NMR spectra are measured with a Bruker AS200 or AS300 (lH NMR at 200 or 300 MHz and 13CNMR at 50.32 or 75.45 MHz) using the solvent as internal standard (6; J (Hz)). The mass spectra refer to data from a Vacuum Generators ZAB instrument (EI, 70 eV). IR spectra were recorded with a Perkin-Elmer 580B. UV light absorption data were recorded using a Varian Cary 17 D or a Hewlett Packard 8452A spectrometer. Elemental analyses: Mikroanalytisches Labor der Universitat Heidelberg. All reactions were carried out in argon atmosphere using dried and oxygen-free solvents. { (1,2,1 1,12-q)-Tricyclo[10.8.0.~~11]eicosa-l,l l-diene-6,16-diol}(q5-cyclopentadienyl)cobaltand {(1,2,11,12-q)Tricycle[10.8.0.02J11eicosa-1,1l-dien-6,17-diol)(q5-cyclopentadieny1)cobalt (17). A 15 g amount (83.3 mmol) of CpCo(C0D) was dissolved in 1.5 L of decalin. The solution was heated t o 150-160 "C. During 6 d 30.4 g (200 mmol) of 16, dissolved in 400 mL decalin, was added. While the addition of 16 was continued, a further portion of CpCo(C0D) was added after 2 d (6.0 g (33.3 mmol)) and after 4d (4.0 g (22.2 "01)). When the addition of 16 was completed, the heating was continued for a further 1 day. The reaction mixture was allowed to cool to room temperature and then filtered through alumina (neutral, grade 111). With pentane as eluent the unreacted CpCo(C0D) could be extracted, while the product 17 remains as a solid at the top of the column. It could be dissolved with some CHzClz and was extracted with ether as a broad yellow band. After the removal of the solvent the crude product was purified by column chromatography (silica gevether). A separation of the isomers of 17 failed, but from the first fractions containing 17 one isomer crystallized as an orange red solid and could be identified by spectroscopic methods. The reaction yielded 17.0 g (40%) of an orange red solid which contained all isomers of 17: mp of the pure isomer 154-155 "C; 'H NMR (300 MHz, CD30D) 6 4.44 (s,5H), 3.723.75 (m, 2H), 2.47-2.59 (m, 4H), 2.20-2.32 (m, 4H), 1.251.90 (m, 20H); 13CNMR (75.45 MHz, CD30D) 6 82.2 (C), 82.0 (C), 81.5 (CH, Cp), 71.9 (CHI, 34.7 (CHz), 32.3 (CHd, 28.5 (CHz), 28.0 (CH2),27.0 (CHz), 24.7 (CHz), 24.5 (CHz);IR (KBr) 2932,2910,1704,1443,1420,1369,1103,997,807; UV (CH3nm (log 6)) 205 (4.401, 228 (4.041, 262 (4.261, 295 CN) (a, (3.161, 377 (2.58); MS (EI, 70 eV) mlz (relative intensity) 429 (0.9), 85 (52), 71 (56), 57 (100),43(84). Anal. Calcd for C25H37Coo2 (428.5): C, 70.08; H, 8.70. Found: C, 69.82; H, 8.80. { (1,2,1l,l2-q)-Tricyclo[ 10.8.0.02J1]eicosa-l,ll-diene-6,16-dione}(q5-cyclopentadienyl)cobalt(18)and { (1,2,11,12-q)-Tricyclo[ 10.8.0.02~11]eicosa-l,l l-diene-6,17-dione}(q5-cyclopentadienyl)cobalt(19). A 17.0 g amount (40 mmol) of 17 and 52.8 g (260 mmol) of aluminum isopropylate were dissolved in toluene (780 mL) and acetone (370 mL). The solution was heated under reflux for 14 h. By checking the reaction with TLC, we noticed in addition to the products and the starting material an intermediately formed monoketone. After the reaction mixture had cooled t o rt (rt = room temperature) 100 mL of water was added and the solution was concentrated in vacuo. To the residue ether and 10% HzS04 were added. The aqueous layer was extracted with ether. The combined organic layers and extracts were washed with saturated NaHC03 solution, dried (MgSOd), concentrated in vacuo, and adsorbed on silica gel. The products were purified by column chromatography (silica geVCHzC12) and yielded 14.0 g (33 mmol) (83%)of an orange red solid. 18: mp 170-172 "C; lH (300 MHz, CDC13) 6 4.42 (s, 5H), 2.96-3.07 (m, 2H), 1.35-2.45 (m, 26H); I3C (75.47 MHz, CDC13) 6 213.3 (C), 80.6 (CH), 79.6 (C), 79.0 (CH), 43.9 (CHz), 36.8 (CHz), 28.6 (CHd, 23.9 (CHz),23.8 (CHz), 23.5 (CHZ),22.0 (CHz);IR (Kl3r) 2932,

Metal-Capped Cyclobutadienophanes 2910, 1704, 1443, 1420, 1369, 1203, 1103, 997, 807; UV and MS are in analogy to those obtained from 19. Anal. Calcd for CzaH3&oO2 (424.47): C, 70.74; H, 7.84. Found: C, 70.87; H, 7.75. 19: mp 147-148 "C; 'H (300 MHZ, CDC13) 6 4.44 (8, 5H), 2.87-2.98 (m, 2H), 2.47-2.56 (m, 2H), 1.33-2.44 (m, 24H); '3C (75.47 MHz, CDCl3) 6 213.3 (C), 80.4 (CH), 79.9 (C), 78.6 (CH),43.4(CHz),37.6 (CHz),37.6 (CH2),27.5 (CH2),24.5 (CHz), 23.8 (CHz, 2 0 , 22.8 (CH2); IR (KBr) 2946, 2908, 1703, 1441, 1422, 1371, 1222, 1102, 821, 805; UV (pentane) (A,-, nm (log E ) ) 266 (4.411, 300 (3.22), 375 (2.73); MS (EI, 70 ev) mlz (relative intensity) 424 (61), 188 (20), 151 (22), 137 (40), 129 (23), 124 (loo), 115 (22), 91 (481, 79 (25), 67 (25), 59 (901, 41 (52). Anal. Calcd for C Z ~ H ~ ~ C(424.47): OOZ C, 70.74; H, 7.84. Found: C, 70.79; H, 7.86. { (1,2,11,12-q)-Tricyclo[ 10.8.0.02~111eicosa-l,ll-diene-6,16-dione bis(semicarbazone)}(qs-cyclopentadienyl)cobalt (20a)and {(1,2,11,12-q)-Tricyclo110.8.0.02J11eicosa1,ll-&ene-6,17-dionebis(semicarbazone)}(q5~clopentadieny1)cobalt (20b). In 250 mL of ethanol were dissolved 10.0 g (90 mmol) of semicarbazideHC1 and 9.0 g (110 mmol) of NaOAc. The solution was refluxed and filtered. The precipitate was washed with hot ethanol. A 12.75 g amount (30 mmol) of the mixed ketones 18 and 19 was added to the combined filtrates, and the solution was refluxed for 45 min. The reaction was controlled by TLC. When the starting material had disappeared, the solvent was removed in vacuo. To the residue were added 500 mL of chloroform and 100 mL of water. The organic layer was separated, washed with saturated NaHC03 solution, and dried (MgS04). After the solvent had been removed 15.1 g of the crude product was obtained as a yellow solid, which could not be recrystallized and was used for the following reaction without any further purification. Bis(selenadiazo1e)s 21 and 22. A 15 g amount (27.9 mmol) of the isomeric mixture of 20 and 10.0 g (90.0 mmol) of SeOz were dissolved in 650 mL of concentrated acetic acid. The mixture was heated for 5-6 h to 30-40 "C. It proved t o be quite dificult to control the progress of the reaction by TLC because of the chromatographical behavior of the starting material. After the reaction was stopped the solvent was removed in vacuo. Chloroform was added t o the residue, and it was neutralized with 5%NazC03 solution. The organic layer was separated, washed with water, dried (MgSOr), and concentrated in vacuo. The mixture of 21 and 22 was chromatographed (silica gellCHzClz), and the product was obtained as a yellow solid, which was used for the following reactions without further purification. { (1,2,11,12-q)-Tricyclo[l0.8.O.02J1leicosa-l,ll-diene-6,17-diyne}(~K-cyclopentadienyl)cobalt (23). A 3.01 g amount (5mmol) of the mixed bis(selenadiazo1e)s 21 and 22 was dissolved in 500 mL of THF. The solution was cooled t o -40 "C. At this temperature 11.0 mmol of BuLi (1.6 M in hexane) was added slowly. The color of the solution changed to deep red, and Nz began to expel. The reaction was monitored by TLC, and the addition of BuLi was continued until no more starting material could be detected. The reaction was quenched with methanol, and the solution was allowed to warm to ambient temperature. Semisaturated NaCl solution, water, 500 mL ether, and some diluted sulfuric acid were added. The organic layer was separated, dried (MgS04), concentrated in vacuo, and adsorbed on silica gel. After column chromatography (silica geVCCl4) and recrystallization from pentane 23 was obtained in a yield of 71% (1.40 g) as a yellow solid: mp 106-108 "C; lH (300 MHz, CDC13) 6 4.49 (s, 5H), 1.5-2.5 (m, 24H); 13C (75.4 MHz, CDCl3) 6 82.3 (C), 82.1 (C), 80.0 (CH), 27.8 (CHz),25.6 (CHz), 19.2 (CH2);IR (CDC13) 2928,2234,1430, 1255,806; UV (pentane) (Ama, nm (log E ) ) 266 (4.38), 296 (3.281, 378 (2.73);MS (EI, 70 eV) mlz (relative intensity) 388 (4), 308 (18), 131 (24), 119 (27), 105 (75), 91 (loo), 57 (18) 43 (18).Anal. Calcd for Cz5H33Co02 (424.47): C, 77.30; H, 7.52. Found C, 77.12; H, 7.57.

Organometallics, Vol. 14, No. 2, 1995 983 { (1,2,12,13-q).Tricyclo[l1.9.0.~~12ldocosa-1,12~&ene-7,18-diol}(q~-cyclopentadienyl)cobalt(24). A solution of

CpCo(C0D) (23.2 g, 100 mmol) in 900 mL of cyclooctane was heated under reflux. During 40 h a solution of 6-cycloundecyn01(16)~~ (16.6 g, 100 mmol) was added. After the addition was completed, the heating was continued for another 20 h. The working up procedure was carried out as described for 17 yielding 16.2 g (72%) of the isomeric mixture of the alcohols (24) as a yellow solid. The isomeric alcohols could be separated by column chromatography (silica gellether), but usually the isomeric mixture was used for further reactions. X-ray studies on single crystals of 24c confirm the given stereochemi~try.~~ { (1,2,12,1S~q)~Tricyclo[ll.9.O.~~1aldocosa-l,12-&ene-7cie,l&cis-diol}(qs.cyclopenta&enyl)cobalt (Ma)(cis/trans defines the relative orientation to the CpCo unit): mp 175 "C; IH (300 MHz, CDsOD) 6 4.53 (s,5H),3.65-3.78 (m, 2H), 2.122.30 (m, 8H), 1.22-1.81 (m, 22H); 13C (75.4 MHz, CD30D) 6 80.9 (CH), 80.7 (C), 72.0 (CHI, 32.9 (CH2), 28.5 (CH2), 25.8 (CHz), 22.6 (CHz); IR (CDCl3) 2924,2848,1267,429; W (CHzIUII (log E ) ) 234 (3.9), 266 (4.2), 300 (3.11, 386 (2.7); Clz) (A, MS (EI, 70 eV) mlz (relative intensity) 456 (481, 189 (lo), 165 (ll), 151 (14), 137 (221,125 (28), 124 (64),41 (100). Anal. Calcd for Cz7H41Co02 (456.22): C, 71.03; H, 9.05. Found: C, 70.89; H, 9.14. { (1,2,12,13-q)-Tricyclo[ 11.9.0.02J21docosa-l,12-diene-7cis,18-trans-&ol}(qs-cyclopenta&enyl)cobalt (24b):mp 162 "C; lH (300 MHz, CD30D) 6 4.55 (8, 5H), 3.62-3.80 (m, 2H), 2.12-2.32 (m, 8H), 1.22-1.78 (m, 22H); I3C (75.47 MHz, CD30D) 6 80.9 (CH), 80.6 (C), 72.7 (CHI, 72.1 (CHI, 32.9 (CHz), 32.7(CH2),28.5 (CH2),27.9(CH2)25.9 (CH2),25.7 (CH2),22.6 (CHz), 22.3 (CH2); IR (CDCl3) 2924,2848, 1036; UV (CHzC12) (A, nm (log E ) ) 234 (4.21, 266 (4.51, 310 (3.51, 378 (3.1); MS (EI, 70 eV) mlz (relative intensity) 456 (411,201 (lo), 189 (ll), 165 (9), 151 (14), 137 (23), 125 (53), 124 (72), 41 (100). Anal. Calcd for C27H41C002 (456.22): C, 71.03; H, 9.05. Found C, 70.90; H, 9.06. {(1,2,12,13-~)-Tricyclo[ll.9.O.02~1aldocosa-l,l2-diene-7trans,18-~ns-&ol}(qs-cyclopenta&enyl)cobalt (24c): mp 182 "C; lH (300 MHz, CD30D) 6 4.55 (s, 5H), 3.63-3.74 (m, 2H), 2.12-2.28 (m, 8H), 1.25-1.80 (m, 22H); (75.47 MHz, CD30D) 6 80.8(CH), 80.6 (C), 72.7 (CHI, 32.7 (CH2),27.9(CHz) 25.9 (CHz),22.4 (CHz); IR (CDC13) 2924,2848,1036; UV (CH2Clz) (A, nm (log E ) ) 234 (4,1), 266 (4.4), 302 (3.2), 378 (2.9); MS (El, 70 eV) mlz (relative intensity) 457 (311,456 (15), 201 (lo), 189 (12), 165 (9), 151 (151,137 (25), 125 (30), 124 (69),41 (100). Anal. Calcd for C ~ ~ H ~ ~ (456.22): C O O Z C, 71.03; H, 9.05. Found: C, 71.03; H, 9.00. { (1,2,12,13-q)-Tricyclo[ll.9.0.~~1aldocosa-l,12-&ene-7,18-dione)(q~-cyclopentadienyl)cobalt (25). A solution of aluminum isopropylate (47.7 g, 234 mmol) and 16.0 g (35.1 mmol) of the mixed alcohols (24)in 1L of toluene and 450 mL of acetone was refluxed for 20 h. The working up procedure was carried out as described for 18/19. Column chromatography on silica gel with a mixture of cyclohexane and ether (1:l)as eluent yielded 13.1 g (83%) of dione 26 as a yellow solid: mp 116 "C; lH (300 MHz, CDCl3) 6 4.55 (8, 5H), 2.472.60 (m, 4H), 2.28-2.42 (m, 4H), 1.97-2.18 (m, 8H), 1.391.78 (m, 16H); I3C (75.47 MHz, CDC13) 6 214.2 (C), 79.9 (CH), 79.2 (C), 40.9 (CHz), 27.8 (CHz), 24.7 (CHz), 23.4 (CH2); IR (CDC13)2930,1700 (C-0), 1257; W (pentane) (A, nm (log E ) ) 206 (4.2), 266 (4.41, 388 (2.7); MS (EI, 70 eV) mlz (relative intensity) 452 ( E ) , 137 (32), 125 (481,124(loo), 91 (54). Anal. Calcd for C Z ~ H ~ ~ (452.23): C O O ~ C, 71.82; H, 8.04. Found: C, 71.76; H, 8.16. { (1,2,12,13-q)-Tricyclo[ 11.9.0.02~181docosa-l,12-&ene-7,18-dione bis(semicarbazone)}(qs-cyclopentadienyl)cobalt (26). The semicarbazide acetate was prepared from 12.0 g (108 mmol) of semicarbazide hydrochloride and 11 g (130 mmol) of sodium acetate as described for 20. A 13.1 g amount (29 mmol) of 25 was added, and the solution was heated under

(23)Gleiter, R.; Langer, H.; Nuber, B. Unpublished results.

984 Organometallics, Vol. 14,No. 2, 1995

Gleiter et al.

2844,1452,1035,899,795; UV (CHzClz) (Am,, nm (log E ) ) 198 reflux for 3 h. The progress of the reaction could be controlled (4.09), 269 (4.17), 296 (3.00), 370 (2.62); MS (EI, 70 eV) mlz by TLC. After the reaction was complete, the solvent was (relative intensity) 400 (40), 137 (28), 124 (701, 121 (661, 107 removed in vacuo. The precipitate was washed with water, (231, 105 (391, 91 (loo), 79 (991, 67 (951, 59 (591, 55 (831, 41 then with saturated NaHC03 solution, again water, and finally (87). Anal. Calcd for C23H33CoOz (400.4): C, 68.99; H, 8.31. with acetone. The reaction yielded 14.7 g (90%)of the isomeric Found: C, 68.81; H, 8.68. mixture of the bis(semicarbaz0ne)s 26 as a yellow solid. The isomers were used as mixture in the following step without { (1,2,10,1 l-q)-Tricyclo[9.7.0.02Joloctadeca-l,10-diene-6further purification. truns,15-cis-diol}(q6-cyclopentadienyl)cobalt(32b): mp 193-197 "C; 'H NMR (300 MHz, CD30D) 6 4.51 (s,5H), 3.50Bis(selenadiazo1e)s27 and 28. A mixture of 14.7 g (26.0 3.70 (m, 2H), 2.14-2.22 (m, 8H), 1.75-1.81 (m, 8H), 1.28mmol) of the isomeric bis(semicarbaz0ne)s 26 and SeO2 (10.0 1.52 (m, 10H); 13C NMR (75.47 MHz, CDC13) 6 80.9 (C), 80.7 g, 90.0 mmol) in 650 mL of concentrated acetic acid was heated (CHI, 79.7 (C), 72.7 (CHI, 68.3 (CHI, 36.9 (CHz), 34.2 (CHz), 3 h t o 40 "C. The procedure was carried out as described for 28.1 (CHz), 25.6 (CH2), 25.4 (CHz),25.3 (CHz);IR (CDC13)3370, 21/22yielding 5.21 g (31.8%)of the isomeric mixture of 27 and nm (log E)) 2920, 2848, 1445, 1034, 798; UV (CH2Clz) (A, 28 as a yellow solid: mp 161 "C (dec); IH (300 MHz, CDC13) 6 195 (4.14), 262 (4.30),296 (3.17),373 (2.64);MS (EI, 70 eV) in 4.53 (s, 5H), 4.52 (s, 5H), 3.28-3.42 (m, 4H), 2.72-3.20 (m, analogy t o those obtained from 32a. Anal. Calcd for C23H3312H), 1.45-2.25 (m, 36H), 0.90-1.15 (m, 4H); 13C(75.47 MHz, Coo2 (400.4): C, 68.99; H, 8.31. Found: 68.31; H, 8.27. CDC13) 6 162.3 (C), 159.5 (C), 79.9 (C), 79.2 (CH), 79.1 (CHI, 76.8 (C), 75.9 (C), 36.1 (CHz), 35.4 (CHz), 28.0 (CHz), 27.9 { (1,2,10,1 l-q)-Tricyclo[9.7.0.@~1010ctadeca-l,10-diene-6trans,15-trans-di01}(~~-cyclopentadienyl)cobalt (32c):mp (CHz), 26.7 (CH2), 26.6 (CH2), 24.4 (CHz), 24.3 (CH21, 23.7 175-184 "C; 'H NMR (200 MHz, CD30D) 6 4.49 (s,5H), 3.80(CH2), 23.5 (CHz), 23.4 (CHz); IR (CDC13) 2926, 2848, 2797, 3.97 (m, 2H), 3.58 (m, 2H), 2.07-2.24 (m, 8H), 1.30-1.80 (m, 1451, 1332, 1310, 1263, 806; UV (CH2Clz) (Am,, nm (log E ) ) 238 (4.11, 266 (4.01, 294 (3.2). Anal. Calcd for C ~ ~ H ~ ~ C O N 16H); ~ S ~13C Z NMR (50.3 MHz, CD30D) 6 80.7 (CH), 80.3 (C), 72.0 (CH), 38.8 (CHz), 28.0 (CHz), 25.8 (CHz);IR (CDCld 3376,2916, (630.44): C, 51.44; H, 5.28; N, 8.89. Found: C, 51.53; H, 5.34; N, 8.01. 2848, 1450, 1103, 1062; UV (CH2Clz) (A, nm (log E)) 195 { (1,2,12,13-q)-Tricyclo[ 11.9.0.02J21docosa-l,12-diene-6,- (4.14), 262 (4.29), 296 (3.02), 372 (2.67); MS (EI, 70 eV) in analogy to those obtained from 32a. 18-diyne}(q6-cyclopentadienyl)cobalt (29)and { (1,2,12,{ (1,2,10,1 1-q))-Tricyclo[9.7.0.02Joloctadeca-l,l0-diene-6,13-q)-Tricyclo[ll.9.O.@~12ldocosa-l,l2-diene-6,l7-diyne}15-dione}(q~-cyclopentadienyl)cobalt (33). A solution of (q5-cyclopentadienyl)cobalt(30). To a cold solution (-40 aluminum isopropylate (46.2 g, 227 mmol) and 14.0 g (35.1 "C) of the mixture of 27 and 28 (5.10g, 8.10 mmol) in 500 mL mmol) of the mixed alcohols 32 in 650 mL of toluene and 320 of THF was added dropwise 21 mmol BuLi (1.6 M solution in mL of acetone was refluxed for 20 h. The following procedure hexane) during 30 min. The color of the solution turns to red, was carried out as described for 18/19. Column chromatogand Nz expels. The reaction was quenched with 10 mL of raphy on silica gel with a mixture of cyclohexane and ether methanol and 10 mL of water. After the addition of 500 mL (1:l) as eluent yielded 9.7 g (71%) of dione 33 as yellow solid: of ether and 100 mL of 10% H2S04 the layers were separated mp 144-145 "C; IH NMR (300 MHz, CDC13) 6 4.47 (s, 5H), and the organic layer was washed with half-concentrated 2.62-2.71 (m, 4H), 2.22-2.36 (m, 8H), 1.76-2.04 (m, 12H); sodium chloride solution. The organic layer was dried ( M g 13CNMR (75.46 MHz, CDC13) 6 214.1 (C) 79.7 (CH), 79.2 (C), sod),the solvent was removed in vacuo, and the residue was 42.1 (CHZ),25.4 (CHz),24.9 (CHz);IR (CDCl3) 2932, 1700, 1439, adsorbed on silica gel. Column chromatography on silica gel nm (log E)) 227 (4.311, 278 with C c 4 as eluent yielded 2.68 g (75%) of the mixture of the 1100, 999, 787; W (CHZClz) (A, (3.871, 325 (3.371, 395 (2.94); MS (EI, 70 eV) mlz (relative two isomeric products as a yellow solid. All attempts to separate the two alkynes by chromatography or crystallization intensity) 396 (1001, 330 (301, 137 (281, 124 (681, 91 (361, 59 (32). Anal. Calcd for CZ~H~ICOOZ (396.4): C, 69.69; H, 7.37. failed. The following physical data were obtained from the mixture of the alkynes: IH (300 MHz, CDC13) 6 4.615 (s, 5H), Found: C, 69.63; H, 7.34. 4.612 (s, 5H), 1.98-2.32 (m, 32H), 1.41-1.88 (m, 24H); l3C { (1,2,10,1 l-q)-Tricyclo[9.7.0.~1010ctadeca-l,10-diene-6,(75.47 MHz, CsDs) 6 83.0 (C), 81.0 (c),80.9 (C), 79.9 (c),79.7 15-dione bis(semicarbazone)}(q6-cyclopentadienyl)co(CH), 79.3 (C), 79.1 (C), 29.3 (CHz), 29.2 (CHz), 29.0 (CH2), balt (34). The semicarbazide acetate was prepared from 22.3 28.8 (CH2), 25.2 (CHz), 25.1 (CHz), 25.0 (CH2), 24.95 (CHz), g (200 mmol) of semicarbazide hydrochloride and 14.2 g (210 24.9 (CHz), 24.8 (CHz), 19.7 (CH2), 19.5 (CH2), 17.8 (CHz); IR mmol) of sodium acetate as described for 20. A 4.0 g amount (CDC13) 2924, 2850, 1429, 802; UV (CH2Clz) (A, nm (log E ) ) (10.4mmol) of 33 was added, and the solution was heated 266 (4.11, 286 (4.1), 376 (2.9); MS (EI, 70 eV) mlz (relative under reflux for 4 d. The progress of the reaction could be intensity) 416 (301,165 (241,141 (241,125 (461,124 (100).Anal. controlled by TLC. After the reaction was complete, the Calcd for Cz7H33Co (416.49): C, 78.05; H, 7.76. Found: C, solvent was removed in vacuo. The precipitate was washed 77.78; H, 7.99. with water, then with saturated NaHC03 solution, again with { ( 1,2,10,11-q)-Tricyclo [9.7.0.@J01 octadeca-l,lO-diene-6,- water, and finally with acetone. The reaction yielded 4.54 g (88%)of the isomeric mixture of the bis(semicarbaz0ne)s 34 15-diol}(qs-cyclopentadienyl)cobalt (32). A solution of as a yellow solid. The isomers were used as a mixture in the CpCo(C0D) (30.5 g, 132 mmol) in 200 mL of decalin was following step without further purification. heated to 160 "C. During 13 d a solution of 29.5 g (214 mmol) of 5-cyclononynol(31) in 2000 mL of decalin was added. After Bis(selenadiazo1e) 35. A mixture of the isomeric bisthe addition was completed, the heating was continued for (semicarbaz0ne)s 34 (2.20 g, 4.30 mmol) and 1.30 g (12.3 mmol) another 30 h. The working up procedure was carried out as in 100 mL of concentrated acetic acid was heated 1 h at 70 described for 17 yielding 14.4 g (34%) of the isomeric mixture "C. The working up procedure was carried out as described of the alcohols (32)as a yellow solid. The isomeric alcohols for 21/22yielding 503 mg (20%) of 35 as a yellow solid: mp could be separated by column chromatography (silica gel/ 176 "C (dec); 'H NMR (300 MHz, CDC13) 6 4.47 (s, 5H), 3.05ether), but usually the isomeric mixture was used for further 3.53 (m, 4H), 1.25-2.98 (m, 16H); 13C NMR (75.47 MHz, reactions. CDC13) 6 160.3 (C), 158.5 (C), 79.7 (CHI, 78.0 (C), 76.4 (CH), 29.9 (CHz), 29.2 (CHz), 26.7 (CHz), 25.0 (CH21, 22.8 (CHz); IR { ( 1,2,lO,ll-q )-Tricyclo[9.7.0.02Joloctadeca-1,lO-diene-g(neat) 2910, 2838,1444, 1344,1312,1263,855,816,809; UV cis, 15-cis-diol) (q6-cyclopentadienyl)cobalt(32a)(citdtrans (CHzClz) A,, nm (log E) 226 (4.01, 238 (4.01, 266 (4.01, 300 defines the relative orientation t o the CpCo unit): mp 194(3.31, 376 (2.4); MS (EI, 70 eV): 360 (29, M+ - N4Sez), 164 204 "C; 'H NMR (300 MHz, CDC13) 6 4.54 (s, 5H), 3.85 (m, (18), 153 (X), 152 (E),128 (231,124 (711,115 (42),84(55),59 2H), 2.04-2.19 (m, 8H), 1.70-1.77 (m, 8H), 1.20-1.50 (m, (100). Anal. Calcd for C ~ ~ H ~ I C (630.44): O N ~ S ~C,~48.10; H, 10H);13CNMR (50.3 MHz, CD30D) 6 80.5 (CH), 80.0 (C),68.3 4.39; N, 9.76. Found: C, 47.89; H, 4.46; N, 9.53. (CHI, 34.1 (CH2),25.4(CH2),25.2 (CHz);IR (CDC13) 3398, 2916,

Metal-Capped Cyclobutadienophanes

Organometallics, Vol. 14, No. 2, 1995 985

{ (1,2,10,11-q~-Tricyclo[9.7.0.W1010dadeca-l,10-diene-6,- some CpCo(CO)2 was added because the trimerization catalyst reacts partially with 23 to yield 2. After 24 h 23 could not be 15-diyne}(q5-cyclopentadienyl)cobalt(36). To a cold soludetected anymore by TLC and the reaction was stopped. The tion (-55 "C) of 350 mg (0.61 mmol) of 35 in 65 mL of THF reaction mixture was concentrated in vacuo, adsorbed on silica was added dropwise 1.3 mmol BuLi (1.6 M solution in hexane) gel, and twice chromatographed (silica gel/pentane:ether = 1:l) during 7 min. The color of the solution turns to red, and Nz to yield 41 as a yellow oil that solidified when pentane was expels. The reaction was quenched by 5 mL of methanol and added. In this way 26 mg (5%)of 41 were obtained as a yellow 5 mL of water. The working up procedure was carried out as solid mp 175-179 "C; lH (300 MI-Iz, c a s ) 6 4.38 (s,5H), 3.50 described for 23 yielding 161 mg (73%)of 36 as a yellow solid: (s,6H), 3.06-3.19 (m, 2H), 2.79-2.88 (m, 2H), 2.52-2.62 (m, mp 155 "C; IH NMR (300 MHz, CDC13) 6 4.55 (8, 5H), 1.372H), 2.26-2.43 (m, 4H), 2.06-2.11 (m, 4H), 1.66-1.99 (m, 3.25 (m, 20H); 13C NMR (75.47 MHz, CDC13) 6 86.1 (C), 85.5 10H); "C (75.47 MHz, C&) 6 169.6 (c), 141.2 (c),135.6 (c), (C), 83.6 (C), 79.8 (CH), 78.7 (C), 30.9 (CHz), 28.3 (CHz), 26.1 130.2 (C), 80.5 (CHI, 80.4 (C), 77.8 (C), 51.8 (CH31, 27.8 (CHz), (CHz), 19.9 (CHz), 19.4 (CHz); IR (CDC13) 2922, 2844, 1433, 26.8 (CHz), 26.2 (CHz), 24.9 (CHz), 23.4 (CH2), 22.1 (CHz); IR nm (log E) 266 (4.3), 1312, 1259, 1014,807; UV (pentane) I,,

(CDC13) 2928,2848,1737,1707,1432,1266,1220,1195,1177; UV (CH3CN) (A,, IUXI(log E ) ) 196 (4.15),266 (4.06),294 (3.25); HRMS (EI, 70 eV) calcd for C31H35C004 mlz 530.1867, found mlz 530.1913. { q4:q4-[34i Cyclobutadienophane)bis(qs-cyclopentadi{ q4:q4-[4,4,3,3]Cyclobutadienophane}bis[ (q5-cyclopeneny1)cobalt (2)and Cyclobutadienoquinonosuperphane tadieny1)cobalt (42), {(7,8,18,19-q)-Hexacyclo[17.3.0. (4). In 80 mL of octane was dissolved 180 mg (1.0 mmol) of 01J3.W~.W12.0~J8]docosa-6,12,18-triene} (q5-cyclopentadiCpCo(CO)z, and while refluxing, the solution of 23 (195 mg, eny1)cobalt (43) and { (6,7,18,19-q 1-Hexacyclo[17.3.0. 0.5 mmol) in 25 mL of octane was added during 90 min. A 01~13.0a~~.W1~.0B~18]docosa-7,12,18~triene} (q5-cyclopentadifew minutes after the addition was finished, no starting eny1)cobalt (44). The solution of 1.01 g (2.42 mmol) of the material (23)could be detected anymore by TLC. After the mixture of the alkadiynes 29130 and 1.80 g (10 mmol) of CpCoreaction mixture had cooled to rt it was concentrated in vacuo (COz) in 250 mL of cyclooctane was heated under reflux for 5 and adsorbed on alumina (neutral, grade 111). The products h. The solvent was removed in vacuo, and the residue was were purified by column chromatography (alumina neutral, adsorbed on alumina (neutral, 10% water). Column chromagrade 111). With pentane as eluent 205 mg (80%) of 2 is tography on alumina (neutral, 10%water) with 40165 petroobtained as a n orange red solid. After 2 is extracted comleum ether yielded first the two bicyclooctatrienes 43 and 44 pletely the eluent was changed to CHzClz and 3 mg (1%)of 4 in a red brown band, which was followed by the yellow band was extracted. The analytical data for 2 and 4 are identical of the cyclobutadienophane 42. The removal of the solvent with those described in the l i t e r a t ~ r e . ~ , ~ yielded 332 mg (26%)of 42 as an yellow solid and 260 mg (26%) { q4:q4-[341Cyclobutadienophane} (q5-cyclopentadieny1)of a mixture of 43 and 44 as a yellow red solid. The separation (q5-pentamethylcyclopentadienyl)cobalt (39). In 100 mL of the two isomeric bicyclooctatriene derivatives failed with of decalin were dissolved 195 mg (0.4mmol) of 23 and 250 mg the exception of the isolation of one single crystal of 44. (1 mmol) of Cp*Co(CO)z,and the solution was heated at 150Analytical data for 42: mp > 250 "C; IH (200 MHz, CDC13) 6 160 "C. The reaction was stopped after 24 h, and the mixture 4.37 (s, lOH), 2.15-2.51 (m, 16H), 1.57-1.75 (m, 4H), 1.45was allowed t o cool to ambient temperature, concentrated in 1.55 (m, 8H); l3C (75.47 MHz, CsDs) 6 81.7 (c), 81.0 (CHI, 80.8 vacuo, adsorbed on alumina (neutral, grade 111), and chro(C), 29.5 (CHz), 28.7 (CHz), 28.6 (CHz), 26.9 (CHz); IR (CDC13) matographed (alumina neutral, grade IIVpentane). The col2916,2886, 2826, 1503, 1262; UV (pentane) (A,=, nm (log E ) ) umn chromatography was repeated, and &r recrystallization 222 (4.3), 284 (4.7), 382 (4.0); MS (EI, 70 eV) mlz (relative from pentane 245 mg (84%)of 39 is obtained as a red solid: intensity) 540 (19), 416 (13), 415 (27), 189 (40), 125 (49), 124 mp > 300 "C; lH (300 MHz, CDC13) 6 4.56 (s, 5H), 2.21-2.25 ~ C O Z C, 71.12; H, 7.09. (100). Anal. Calcd for C ~ ~ H ~ (540.51): (m, 8H), 1.80-1.84 (m, 8H), 1.76 (15H), 1.52-1.61 (m, 8H); Found: C, 70.97; H, 7.11. Analytical data for the mixture of 13C (75.47 MHz, CDC13) 6 87.0 (C), 80.3 (CH), 78.5 (C), 74.0 43 and 44: mp 220 "C; lH (300 MHz, CDCl3) 6 4.43 (s, 5H), (C), 28.0 (CHz), 26.9 (CHz), 25.0 (CHz), 9.5 (CH3); IR (KBr) 4.32 (s,5H), 2.73-2.81 (m, 8H), 1.22-2.30 (m, 48H); 13C(75.47 2922,2886,1443,1376,1342,994,549,495;UV (hexane) (Im,, MHz, C&) 6 1.54.4 (c), 154.0 (c),90.2 (c), 87.5 (c),86.0 (c), nm (log E)) 205 (3.75),243 (3.351, 399 (4.05); MS (EI, 70 eV) 83.3 (CH), 81.9 (CH), 66.8 (C), 66.0 (C),38.0 (CHz), 35.9 (CH2), mlz (relative intensity) 582 (lo),457 (27), 291 (221,259 (1001, 133 (34), 124 (251, 59 (32). Anal. Calcd for C~SHUCOZ 35.5 (CHz), 35.3 (CHz), 31.0 (CHz), 30.2 (CHz), 29.2 (CHz), 28.8 (CHz), 28.5 (CHz), 28.3 (CHz), 26.7 (CHz), 26.6 (CHz), 26.3 (582.60): C, 72.16; H, 7.61. Found: C, 72.36; H, 7.57. (CHz), 25.9 (CHz), 25.8 (CHz), 25.3 (CH2), 25.2 (CHz), 24.4 { q4:q4-[34]Cyclobutadienophane}(q5-cyclopentadien(CHz); IR (CDCl3) 2930, 2916, 2880, 2846, 1441, 807; UV y1)cobalt (Irontricarbonyl)(40). In 200 mL of toluene were (pentane) (A, nm (log E)) 228 (4.35), 290 (4.01, 396 (2.95). dissolved 195 mg (0.5 mmol) of 23 and 117 mg (0.6 mmol) of Anal. Calcd for C Z ~ H ~(416.49): ~ C O C, 78.05; H, 7.76. Found: Fe(C0)5, and the solution was refluxed. After 5 h once again C, 77.94; H, 7.90. 117 mg of Fe(C0)b was added, and the heating was continued. X-rayCrystallography and Structure Solution. Data After 12 h 23 could not be detected anymore by TLC. The were collected on a Syntex R3 (23,36,and 44)or a Siemens reaction mixture was allowed t o cool to ambient temperature. Stoe AEDII diffractometer (40)at room temperature. Relevant It was concentrated in vacuo, adsorbed on silica gel and crystal and data collection parameters are given in Table 1. chromatographed (silica gellpentane). The column chromaThe structures were solved by using standard Patterson tography was repeated, and after recrystallization from penmethods, least-squares refinement, and Fourier techniques. tane 22 mg (8.3%)of 40 was obtained as a yellow solid: mp > All calculations were performed with the SHELXTL PLUS 300 "C; 'H NMR (300 MHz, C&) 6 4.46 ( 8 5H), 2.05-2.13 program.24 (m, 16H), 1.33-1.43 (m, 8H); 13C (75.47 MHz, CsD6) 6 217.4 C&I&o (23). A yellow crystal of the dimensions of 0.3 x (C), 87.3 (C), 80.5 (CH), 78.7 (C), 28.1 (CHz), 26.3 (CHz), 25.6 0.5 x 0.5 mm3 was obtained from pentane at -8 "C. The unit (CHz); IR (C&) 2936, 2894, 2006, 1944, 1429, 1349, 1248, cell was determined and refined from 25 reflections (16.0 < 1103, 1070, 736,702,605; UV (pentane) (I,,, nm (log E)) 202 28 < 29.00). (4.62),240 (4.22),288 (4.61);HRMS (EI, 70 eV) calcd for C=HzsCoFeO3 mlz 528.0798, found mlz 528.0780. CmH25Co (36). A yellow crystal of the dimensions of 0.08 x 0.25 x 0.30 mm3 was obtained from pentane at -30 "C. The Cyclobutadienoarenophane (41). In 200 mL of toluene were dissolved 388 mg (1.0 mmol) of 23,20 mg of CpCo(CO)z, and 2.84 g (20 mmol) of dimethyl acetylenedicarboxylate (24) SHELXTL PLUS (release 3.41, Siemens Analytical X-Ray Instruments, 1989. (DMAD), and the solution was refluxed. During the reaction 296 (3.1),376 (2.6);MS (EI, 70 eV) 360 (1001,259 (9),233 (16), 231 (141, 207 (9), 193 (lo), 124 (24); HRMS (EI, 70 eV) calcd for C~3Hz&o,mlz 360.1289, found mlz 360.1342.

986 Organometallics, Vol. 14,No. 2, 1995 unit cell was determined and refined from 24 reflections (5.0 < 28 16.00). CasHssCoFeOs (40). A Yellow crystal of the dimensions of 0.16 x 0.76 x 0.76 mm3 was obtained from pentane at -8 "C. The unit cell was determined and refined from 27 reflections (8.0 28 < 27.00). c z , ~ s c(4o4). A brown-red crystalof the dimensions of 0.15 x 0.30 x 0.90 mm3 was obtained from pentane at 20 OC. The unit cell was determined and refined from 25 reflections (5.0 < 2-9 < 24.00).

Gleiter et al.

Acknowledgment. We are grateful to the Deutsche Forschungsgemeinschaft (SFB 247), the Fonds der Chemischen Industrie, and the BASF AktiengesellschaR for financial s u p p o ~ . Supplementary Material Available: Tables 51-512, listing the distances, angles, and anisotropic thermal parameters for non-hydrogen atoms (17 pages). Ordering information is given On any current masthead page. OM940759H