Spiro-fused cyclopentadienes and novel pyridinium carbonyltungstates from (1-alkynyl)carbene tungsten complexes and exo-methylene n-heterocycles. Competition between 1,4-addition, 1,2-addition, and metathesis

Organometallics 2001, 20, 2889-2904

2889

Sp ir o-F u sed Cyclop en ta d ien es a n d Novel P yr id in iu m

Ca r bon yltu n gsta tes fr om (1-Alk yn yl)ca r ben e Tu n gsten

Com p lexes a n d exo-Meth ylen e N-Heter ocycles.

Com p etition betw een 1,4-Ad d ition , 1,2-Ad d ition , a n d

Meta th esis¹

I. Go¨ttker-Schnetmann, Rudolf Aumann,* Olga Kataeva,^†Christiane Holst,^†and

Roland Fro¨hlich^†

Organisch-Chemisches Institut der Universita¨t Mu¨nster, Corrensstrasse 40,

D-48149 Mu¨nster, Germany

Received February 13, 2001

Reaction of (1-alkynyl)carbene tungsten complexes 1a -c with different exo-methylene

N-heterocycles was found to yield 1,4- and 1,2-adducts as well as metathesis products in

ratios depending on structural details. 2-Methyleneindoline 2a gave conjugated metalla-

hexatrienes 4a ,c and cross-conjugated metallahexatrienes 3a ,c by 1,4-addition and metath-

esis, respectively. Cross-conjugated metallahexatrienes were shown to be thermally trans-

formed in conjugated metallahexatrienes by a skeletal rearrangement. 2-Propenylideneindolines

2b-d afforded cross-conjugated metallaoctatetraenes 8 and 9 resulting from metathesis of

the exo-propenylidene moiety at the 1,2- and the 3,4-double bond position, respectively.

2-Methylene-1,2-dihydropyridines 12a,b and 4-methylene-1,4-dihydropyridines 13c-e yielded

conjugated metallaoctatetraenes 14 and 15 in each case by 4-addition, which underwent a

π-cyclization to spiro compounds 16 and 17, respectively. 4-Methylene-1,4-dihydropyridines

13f,g afforded no 4-addition products but novel pyridinium carbonylmetalates 18 by

2-addition.

In tr od u ction

tion was provided more recently. Reactions of (1-alkynyl)-

carbene tungsten complex 1a with cycloalkenylamines

(Chart 1) were shown to produce both conjugated

metallahexatrienes C by 4-addition (path b) and cross-

conjugated metallahexatrienes B by metathesis (path

a).^5,6Evidence for the intermediacy of (aminocyclo-

butenyl)carbene complexes A in this reaction could be

(1-Alkynyl)carbene complexes have been used as

stoichiometric reagents in a number of high-yielding

reactions of potential use to organic synthesis.²For

example, addition of (1-alkynyl)carbene complexes to

cycloalkenylamines has been shown to provide an ef-

ficient entry into the formation of cyclopentadienes. The

latter compounds were found to result from π-cyclization

of 1-metalla-1,3,5-hexatriene³precursors, which were

generated by a Michael-type 4-addition of the enamine

to the corresponding (1-alkynyl)carbene complex.⁴More

detailed information on the course of this transforma-

(5) (a) Aumann, R.; Roths, K.; La¨ge, M.; Krebs, B. Synlett 1993, 667-

669. (b) Aumann, R.; Roths, K.; Fro¨hlich, R. Organometallics 1997,

16, 5893-5899. (c) Aumann, R. Ko¨ssmeier, M.; J a¨ntti, A. Synlett 1998,

1120-1122. (d) Aumann, R.; Go¨ttker-Schnetmann, I.; Fro¨hlich, R.;

Meyer, O. Eur. J . Org. Chem. 1999, 2545, 5-2561 and 3209.

(6) Different results are obtained from reactions of (1-alkynyl)-

carbene complexes with enol ethers or silylenolethers: Instead of

Michael-type adducts, products obtained by a ene-type reaction have

* To whom correspondence should be addressed. Fax: ++49 251

833 6502. E-mail: aumann@uni-muenster.de.

been reported in a few cases. However formation of (alkoxy- or

siloxycyclobutenyl)carbene complexes which in some cases yielded

metathetical products () cross-conjugated metallatrienes) by cyclo-

reversion reaction has been reported: (a) Faron, K. L.; Wulff, W. D. J .

Am. Chem. Soc. 1988, 110, 8727-8729. (b) Camps, F.; Moreto´, J . M.;

Ricart, S.; Vin˜as, J . M.; Molins, E.; Miratvitlles, C. J . Chem Soc., Chem.

Commun. 1989, 1560-1562. (c) Faron, K. L.; Wulff, W. D. J . Am. Chem.

Soc. 1990, 112, 6419-6420. (d) Camps, F.; Llebar´ıa, A, Moreto´, J . M.;

Ricart, S.; Vin˜as, J . M. Tetrahedron Lett. 1990, 31, 2479-2482. (e) de

Meijere, A.; Kaufmann, A.; Lackmann, R.; Militzer, H.-Ch.; Reiser, O.;

Scho¨menauer, S.; Weier, A. In Organometallics in Organic Synthesis

II; Werner, H., Erker, G., Eds.; Springer: Berlin, 1989; pp 255-276.

(f) Merlic, C. A.; Xu, D. J . Am. Chem. Soc. 1991, 113, 7418-7420. (g)

Pipoh, R.; van Eldik, R.; Wang, S. L. B.; Wulff, W. D. Organometallics

1992, 11, 490-492. (h) Camps, F.; J ordi, L.; Moreto´, J . M.; Ricart, S.

J . Organomet. Chem. 1992, 436, 189-198. (i) J ordi, L.; Moreto´, J . M.;

Ricart, S.; Vin˜as, J . M. J . Organomet. Chem. 1993, 444, C28-C30. (j)

J ordi, L.; Camps, F.; Ricart, S.; Vin˜as, J . M.; Moreto´, J . M.; Mejias,

M.; Molins, E. J . Organomet. Chem. 1995, 494, 53-64. (k) Wulff, W.

D.; Faron, K. L.; Su, J .; Springer, P.; Rheingold, A. L. J . Chem. Soc.,

Perkin Trans. 1 1998, 197-219. (l) Aumann, R.; Hildmann, B.;

Fro¨hlich, R. Organometallics 1998, 17, 1197-1202. For the production

of “ene” products from reactions of (1-alkynyl)carbene complexes with

certain cyclic enamines see: ref 3d; ref 3e; ref 9.

^†X-ray structure analyses.

(1) Part 111 of the series Organic Synthesis via Transition-Metal

Complexes. For part 110 see: Wu, H.; Aumann, R.; Fro¨hlich, R.;

Wegelius, E. Organometallics 2001, 20, in press.

(2) For a review on the chemistry of (1-alkynyl)carbene complexes

see: Aumann, R.; Nienaber, H. Adv. Organomet. Chem. 1997, 41, 163-

242.

(3) For

a recent review on the chemistry of 1-metalla-1,3,5-

hexatrienes see: (a) Aumann, R. Eur. J . Org. Chem. 2000, 17-31. For

related chemistry based on the insertion of alkynes into (â-aminoalk-

enyl)carbene complexes see: (b) de Meijere, A. Pure Appl. Chem. 1996,

68, 61-72. (c) de Meijere, A.; Schirmer, H.; Duetsch, M. Angew. Chem.

2000, 112, 4124-4162; Angew. Chem., Int. Ed. 2000, 39, 3964-4002.

(d) Go¨ttker-Schnetmann, I.; Aumann, R. Organometallics 2001, 20,

346-354. (e) Flynn, B. L.; Schirmer, H.; Duetsch, M.; de Meijere, A.

J . Org. Chem. 2001, 66, 1747-1754.

(4) (a) Aumann, R.; Roths, K.; Grehl, M. Synlett 1993, 669-671. (b)

Aumann, R.; Ko¨ssmeier, M.; Roths, K.; Grehl, M. Synlett 1994, 1041-

1044. (c) Meyer, A. G.; Aumann, R. Synlett 1995, 1011-1013. (d)

Aumann, R.; Meyer, A. G.; Fro¨hlich, R. Organometallics 1996, 15,

5018-5027. (e) Aumann, R.; Ko¨ssmeier, M.; Zippel, F. Synlett 1997,

621-623.

Publication on Web 06/01/2001

2890 Organometallics, Vol. 20, No. 13, 2001

Go¨ttker-Schnetmann et al.

Ch a r t 1. F or m a tion of Cr oss-Con ju ga ted Meta lla tr ien es B a n d Th eir Con ver sion in to Con ju ga ted

Meta lla tr ien es C Accor d in g to Ref 5c

Sch em e 1. F or m a tion of Cr oss-Con ju ga ted Meta lla tr ien es 3 a n d Con ju ga ted Meta lla tr ien es 4 fr om

exo-Meth ylen ein d olin e 2a a n d Tr a n sfor m a tion of Cr oss-Con ju ga ted in to Con ju ga ted Meta lla tr ien es

provided by a crystal structure analysis.⁷Most interest-

ingly, it was shown that cross-conjugated metallatrienes

B could be transformed into conjugated metallatrienes

C, apparently by (reversible) formation of (aminocyclo-

butenyl)carbene complexes A. Thermolysis of cross-

conjugated metallatrienes B thus also resulted in

formation of cyclopentadienes D (Chart 1).^5c,8

Ring strain had been implied as the driving force for

the transformation of cross-conjugated metallatrienes

B into conjugated metallatrienes C.^5c,9Up to date

however, simple rules predicting whether conjugated or

cross-conjugated metallatrienes would be obtained in

these reactions are still lacking, even though only one

isomer of the one or the other kind was observed in most

cases.^4,5a,b,dIt appears that the competing reaction paths

leading to the formation of metathesis products and

Michael-type adducts, respectively, is very sensitive to

minor changes of reactant structures as well as reaction

conditions. Here we wish to report on reactions of exo-

methylene N-heterocycles with (1-alkynyl)carbene com-

plexes 1 which may be considered borderline cases, since

they afford as well 4-addition products as metathesis

products of an enamine unit and beyond these also

pyridinium carbonylmetalates resulting from an up to

date only rarely reported 2-addition to an (1-alkynyl)-

carbene complex.

Meta th esis of th e (N)CdCH₂Un it of exo-Meth -

ylen ein d olin e. The addition of exo-2a to (1-alkynyl)-

carbene complexes 1 in a temperature range -20 to 20

°C affords mixtures of conjugated 1-metalla-1,3,5-trienes

4 (path b) and cross-conjugated metallatrienes 3 (path

a) (Scheme 1). From compound 1a (R ) Ph) both types

of metallatrienes, 3a and 4a , could be isolated. It was

shown that the product ratio 3a :4a was dependent not

only on the solvent but also on the concentration of the

(7) A ring-opening of a (aminocyclobutenyl)carbene carbene complex

to a conjugated 1-metalla-1,3,5-hexatriene is reported by: Aumann,

R.; Hildmann, B.; Fro¨hlich, R. Organometallics 1998, 17, 1197-1201.

(8) Another example for the interconversion of (cyclic) cross-

conjugated into conjugated metallatrienes and subsequent transforma-

tion is reported by: Aumann, R.; Ko¨ssmeier, M.; Roths, K.; Fro¨hlich,

R. Tetrahedron 2000, 56, 4935-4949.

(9) Aumann, R.; Ko¨ssmeier, M.; Mu¨ck-Lichtenfeld, Ch.; Zippel, F.

Eur. J . Org. Chem. 2000, 37-49.

Spiro-Fused Cyclopentadienes

Organometallics, Vol. 20, No. 13, 2001 2891

Sch em e 2. Ald eh yd e 7a by Hyd r olysis of

Com p ou n d 3a

reaction mixture. It was also influenced by the presence

of triethylamine. For example, reaction of compound 1a

(R ) Ph) in diethyl ether or dichloromethane in a con-

centration of 0.25 mol/L gave a mixture of compounds

3a and 4a in a ratio of ca. 1:1, but in n-pentane under

otherwise similar conditions this product ratio was

changed to ca. 3:2. In more dilute reaction mixtures of

0.01 mol/L in diethyl ether a product ratio of ca. 10:1

could be achieved, if 0.05 mol/L of triethylamine was

added. Compound 1b (R ) Me₃Si) under similar condi-

tions afforded only a conjugated metallatriene 4b, but

no cross-conjugated product, while compound 1c (R )

cyclohex-1-enyl) gave only a cross-conjugated metalla-

triene 3c but no conjugated metallatriene 4c, indepen-

dent of the concentration of the reactants, the solvent,

and the presence or absence of triethylamine (Scheme 1).

A thermally induced conversion of a cross-conjugated

metallatriene B into a conjugated metallatriene C, as

outlined in Chart 1 for cyclic compounds, was found also

for open-chain derivatives 3 and 4. For example, it was

shown by NMR spectra that the conjugated metalla-

triene 4a was transformed into the spiro-fused¹⁰cyclo-

pentadiene 6a at 55 °C, C₆D₆(in a sealed NMR tube,

10 h in 77% isolated yield). Interestingly, compound 6a

was also obtained from the corresponding cross-conju-

gated metallatriene 3a at 70 °C, C₆D₆(sealed NMR

tube), 60 h in similar yields (Scheme 1). It could be

metallatriene 3c (R ) cyclohex-1-enyl) was not trans-

formed into the cyclopentadiene 6c even at 80 °C in

toluene-d₈in a sealed NMR tube after 60 h, but gave a

very stable tetracarbonyl chelate complex 5c instead

(Scheme 1).

Str u ctu r e Elu cid a tion of Com p ou n d s 3-7. Char-

acteristic of compounds 3 are ¹³C NMR signals of the

dCH₂group at δ 123.0 (3a ) and 120.1 (3c), (broad)

signals of (OC)₅WdC(OEt)C(R)dCN at δ 176.8 (3a ) and

177.4 (3c), and (broad) signals of the WdC unit in a

range δ 270-266 (3a ) and 269-266 (3c). The connec-

tivty of the ligand backbone of compounds 3a ,c is in

accordance with GHSQC and GHMBC experiments.

Furthermore, it was shown that hydrolysis of compound

3a on silca gel afforded an aldehyde 7a , which was

identified by a crystal structure analysis (Scheme 2).^5d,11

Crystals suitable for a crystal structure analysis were

not available for cross-conjugated metallatrienes 3 but

could be obtained of conjugated metallatriene 4a from

diethyl ether at -40 °C. The molecular structure of

compound 4a revealed a trough-shaped (3Z,4-s-cis)-1-

tungsta-1,3,5-hexatriene backbone, which perfectly fits

the geometric requirements for the π-cyclization to a

cyclopentadiene ring. The pattern of alternating bond

distances W-C4 2.267(6), C4-C5 1.411(9), C5-C6

1.393(9), C6-C7 1.436(9), C7-C8 1.361(10), and C8-

N9 1.350(9) Å is in accordance with a significant

π-conjugation within the 6-amino-1-metalla-1,3,5-hexa-

triene moiety.

Spectroscopic features characteristic of cyclopenta-

dienes 6 are the ¹³C NMR signals of the spiro carbon

atom at δ 87.6 (6a ) and 87.9 (6b) as well as the ¹H NMR

signals of the olefinic protons of the cyclopentadiene ring

at δ 6.02, 5.22 (6a ) and δ 6.02, 4.92 (6b) [d each,

⁴J (¹H,¹H) ) 1.7 Hz].

The molecular structure of compound 6a was estab-

lished also by a crystal structure analysis (Figure 3).

It shows a nearly planar cyclopentadiene ring with

C8-C4-C5-C6 1.2(2)°, C4-C5-C6-C7 1.8(2)°,

C5-C6-C7-C8 4.1(2)°, which is spiro-fused to the

slightly twisted N-heterocyclic ring, C8-N9-C110-

C115 21.2(1)°, N9-C110-C115-C12 0.2(1)°, C110-

C115-C12-C8 19.6(1)°, C10-N9-C110-C115 156.0(1)°.

The twisting angle between both rings was found to

be R(C8,C4,C5,C6,C7/C8,N9,C110,C115,C12) ) 91.0°.

The tetracarbonyl chelate complexes 5a ,c were readily

distinguished from the corresponding pentacarbonyl

complexes 3a ,c by a characteristic high-field shift of

the signal of the coordinated olefinic group in both the

¹H and ¹³C NMR spectra. For example, compound 5a :

1

unambiguously shown that the H NMR signals of an

equilibrium mixture of compound 3a and its (CO)₄W

chelate derivative 5a were decreasing, while signals of

the corresponding cyclopentadiene 6a were increasing

in intensity. It was not possible to directly observe

formation of the conjugated metallatriene 4a from the

cross-conjugated compound 3a in the NMR spectra, in

line with the expectation that compound 4a would

undergo a π-cyclization faster than it was generated

from compound 3a by a skeletal rearrangement. The

complete transformation of compound 3a into the cyclo-

pentadiene 6a requires a constant atmosphere of carbon

monoxide, which is provided in a sealed NMR tube. If

the thermolysis of the cross-conjugated metallatriene

3a was performed in an open argon atmosphere at 40

°C, 60 h, it resulted in the loss of 1 equiv of carbon

monoxide to give a very stable tetracarbonyl complex

5a , which was not further transformed into the cyclo-

pentadiene 6a under these conditions even at 70 °C, 60

h. It should be noted that this is the first report on a

skeletal rearrangement of an open-chain cross-conju-

gated metallatriene into a conjugated metallatriene,

thus indicating that ring strain effects imposed in cyclic

systems are not essential for this rearrangement to

occur. Steric repulsion within the (4-aminocyclobutenyl)-

carbene complex seems to favor a proximal ring-opening

(path b, Scheme 1).

The ease of the π-cyclization of metallatrienes 4 is

strongly influenced by the substituents R. Thus com-

pound 4b (R ) SiMe₃), which due to its thermolability

could not be isolated analytically pure, afforded the

cyclopentadiene 6b at 30 °C, 6 h. The cross-conjugated

(10) Formation of spiro-fused cyclopentadienes from (â-amino-

alkenyl)carbene complexes and arylalkynes was recently reported by:

(a) Schirmer, H.; Duetsch, M.; Stein, F.; Labahn, Th.; Knieriem, B.;

de Meijere, A. Angew. Chem. 1999, 111, 1369-1371; Angew. Chem.,

Int. Ed. 1999, 35, 1285-1287. (b) Schirmer, H.; Flynn, B. L.; de Meijere,

A. Tetrahedron 2000, 56, 4977-4984.

(11) (a) Aumann, R.; Hinterding, P.; Kru¨ger, C.; Goddard, R. J .

Organomet. Chem. 1993, 459, 145-149. (b) Aumann, R.; Schro¨der, J .;

Heinen, H. Chem. Ber. 1990, 123, 1369-1374.

2892 Organometallics, Vol. 20, No. 13, 2001

Go¨ttker-Schnetmann et al.

F igu r e 1. Molecular structure of aldehyde 7a . Selected

bond lengths (Å) and angles (deg): N-C7 1.404(2), N-C8

1.380(2), C8-C1 1.547(2), C8-C9 1.378(3), C9-C10 1.445(3),

C10-O 1.223(2), C9-C11 1.498(3), C11-C12 1.323(3),

C11-C13 1.490(3); C7-N-C21 120.2(1), C7-N-C8 111.5(1),

C21-N-C8 127.5(1), N-C8-C9 125.0(1), C8-C9-C10

120.6(1), C8-C9-C11 124.3(1), C9-C10-O 124.1(1), C10-

C9-C11 114.7(1), C9-C11-C12 118.8(1), C9-C11-C13

118.6(1); C7-N-C8-C9 173.3(1), N-C8-C9-C10-171.7(1),

N-C8-C9-C11 13.7(3), C8-C9-C10-O 178.0(2), C8-

C9-C11-C12 66.3(2), C8-C9-C11-C13 115.3(2).

F igu r e 3. Molecular structure of the spiro-cyclopentadiene

6a . Selected bond lengths (Å) and angles (deg): C8-C4

1.528(2), C4-C5 1.339(2), C5-C6 1.477(2), C6-C7 1.349(2),

C7-C8 1.505(2), C8-N9 1.479(2), N9-C110 1.398(2),

C110-C115 1.395(2), C115-C12 1.516(2), C12-C8 1.576(2);

C4-C5-C6 108.0(1), C7-C6-C5 109.4(1), C6-C7-C8

110.4(1), C7-C8-C4 100.9(1), N9-C8-C4 111.2(1),

C4-C8-C12 113.3(1), C7-C8-C12 114.5(1), N9-C8-C7

115.1(1), C115-C12-C8 100.2(1), C110-C115-C12

108.8(1), C115-C110-N9 110.7(1), C110-N9-C8 106.8(1),

C10-N9-C8 116.6(1), C110-N9-C10 119.1(1), N9-C8-

C12 102.3(1); C8-C4-C5-C6 1.2(2), C4-C5-C6-C7 1.8(2),

C5-C6-C7-C8 4.1(2), C8-N9-C110-C115 21.2(1), N9-

C110-C115-C12 0.2(1), C110-C115-C12-C8-19.6(1),

C10-N9-C110-C115 156.0(1).

20 °C, 6 h, affords purple-red metallaoctatetraenes 8

[by metathesis of the (N)CdCHCHdCH unit at the

C1dC2 bond, path d] and brown-red metallatetraenes

9 [by metathesis of the (N)CdCHCHdCH unit at the

C3dC4 bond, path c] (Scheme 3). To our knowledge this

is the first reported case of a metathesis of a 1-amino

butadiene unit at the C3dC4 double bond. It should be

noted that Michael adducts (vide supra) were not

obtained.

The product ratio of compounds 8 and 9 is strongly

influenced by steric factors. Generation of metalla-

tetraenes 8b-d was found to be highly favored for

compounds 2b-d , which bear only one substituent at

the terminal carbon atom of the side-chain. Compounds

9 could not be detected in this case while monitoring

the reaction by NMR spectra, even though trace amounts

of some red-brown compounds were found by TLC tests,

which have an R_fvalue similiar to that of compound

9a . Steric hindrance at the terminal CdC bond of

compound 2a by methyl groups resulted in an overall

retardation of reaction path c and the generation of

noticeable amounts of compound 9a as a byproduct of

the formation of compound 8a (Scheme 3).

Figu r e 2. Molecular structure of 1-metalla-1,3,5-hexatriene

4a . Selected bond lengths (Å) and angles (deg): W-C4

2.267(6), O3-C4 1.323(8), C4-C5 1.411(9), C5-C6 1.393(9),

C6-C7 1.436(9), C7-C8 1.361(10), C8-N9 1.350(9), C6-

C60 1.498(9), C8-C13 1.537(8); O3-C4-W 128.6(5), C5-

C4-W 117.9(5), C6-C5-C4 132.8(6), C5-C6-C60 115.4(6),

C5-C6-C7 129.9(6), C8-C7-C6 131.3(6), N9-C8-C7

128.6(6), C7-C8-C13 122.9(6), C8-N9-C10 126.0(6),

C8-N9-C11 111.2(5), C11-N9-C10 122.2(6); W-C4-

C5-C6 171.3(6), C4-C5-C6-C7 13.9(12), C4-C5-C6-

C60 162.3(7), C5-C6-C7-C8 33.4(12), C6-C7-C8-N9

17.9 (13), C6-C7-C8-C13 165.5(7).

δ(CdCH₂) 95.6 (3a : 146.5), (CdCH₂) 64.9 (3a : 123.0),

(CdCH₂) 4.39 and 4.15 (3a : 6.18 and 5.44). The ¹³C

NMR signals of the WdC unit were observed in the

expected range at δ 269.6 (5a ) and 268.5 (5c) together

with the (CO)₄group for compound 5a at 218.2, 213.6,

208.6, and 208.3 (5c: 216.5, 215.1, 208.6, and 206.6).

Met a t h esis of t h e (N)CdCH CHdCH ₂Un it of

exo-P r op en ylid en ein d olin es Both a t th e Ter m in a l

CdC Bon d . Our studies were extended to reactions of

(1-alkynyl)carbene complexes 1 with 2-(1-propen-3-

ylidene)indolines 2b-d containing a (N)CdCHCHdCH₂

unit in order to study its interaction at both the

C1dC2 and the C3dC4 bond. The latter compounds

were derived from compound 2a by condensation with

isobutyraldehyde, propionaldehyde, and 2-phenylacetal-

dehyde, respectively. They form mixtures of stereoiso-

mers with respect to the (N)CdCH bond [E/ Z ) 9:1

(2b), 7:3 (2c), and 99:1 (2d )], while the terminal CdC

bond exhibits the E-configuration in each case.¹²

Stereochemical information on the structure of com-

pounds 8 was collected by extensive NMR studies. The

¹H NMR spectrum of compound 8c in C₆D₆at 27 °C,

400 MHz, shows two similar sets of signals for its

stereoisomers in a molar ratio of ca. 95:5. Most char-

acteristic are the AB systems resulting from protons

3

NC(R)dCHCHdC(R), J ) 13.0 Hz, δ 9.04 and 6.22 of

3

the major isomer 8c, and J ) 13.0 Hz, δ 9.07 and 6.23

of the minor isomer 8′c. The signal of the NCH₃group

at δ 2.24 for 8c is significantly shifted downfield to δ

3.39 for 8′c by anisotropic effects. The assignment of

signals is based on NOE and ROESY experiments (600

Addition of 2-(1-propen-3-ylidene)indolines 2b-d to

(1-alkynyl)carbene complexes 1a ,c in diethyl ether at

(12) Hubschwerlen, Ch.; Fleury, J .-P. Tetrahedron 1977, 33, 761-

765.

Spiro-Fused Cyclopentadienes

Organometallics, Vol. 20, No. 13, 2001 2893

Sch em e 3. Meta la tetr a en es 8 a n d 9 by Meta th esis of exo-P r op en ylid en e In d olin es 2b-d

Ch a r t 2. NOE Effects In d ica tin g a Slow Ch em ica l Exch a n ge betw een Isom er s 8c a n d 8′c

MHz), since a severe spin-saturation transfer between

the isomers had to be encountered on irradiation of the

signals NC(R)dCHCHdC(R) and NCH₃. Irradiation of

the signal C(CH₃)₂group at δ 1.67 of the major isomer

8c in a ROESY experiment led to a negative intensity

enhancement of a signal at δ 0.87 arising from the minor

isomer 8′c (which due to overlap was not observable in

its ¹H NMR spectrum). ROESY experiments in this

context provided the unambiguous proof for a spin-

saturation transfer, since negative ROE effects do not

exist.¹³The stereochemistry as well as chemical ex-

change reaction between compounds 8c and 8′c was

elucidated by careful studies of spin-saturation transfer,

NOE, and ROE experiments. Most importantly, irradi-

tion of the signal NC(R)dCHCHdC of compound 8c in

an NOE experiment was causing a negative response

of the NCH₃group and a positive response of the

C(CH₃)₂group of 8c, while irradiation of NCH₃of

compound 8c showed a negative response of the NC-

(R)dCHCHdC and a positive response of the NC(R)d

CH-CHdC proton of the same isomer, thus indicating

a cis/ trans isomerization of the NC(R)dCH bond on the

NMR time scale (Chart 2).

Since compounds 8a -d were observed in roughly the

same ratio of 8:8′ ) ca. 95:5 at 300 K in C₆D₆, the

stereochemical information introduced by the E/Z ratio

of the NCdCH bond of compounds 2b-d (i.e., for 2b,

90:10; 2c, 70:30; 2d , 99:1) has been lost in the products

8/8′ by the exchange phenomena discussed before.

Structural information on the stereochemistry of

compounds 8 was further provided by a crystal structure

analysis of compound 8a (Figure 4). The ligand back-

bone W-C6-C7-C10-C11-C12-N13 of compound 8a

in the solid state fits perfectly with the information

derived for the major isomer 8c from NOE and ROESY

experiments.

Sp ir o-Cyclop en ta d ien es 10 by π-Cycliza tion of

Meta lla octa tetr a en es 8. It has been previously dem-

onstrated that compounds 8a -d undergo a π-cyclization

(13) (a) Bothner-By, A. A.; Stephens, R. L.; Lee, J . J . Am. Chem.

Soc. 1984, 106, 811-813. (b) Bax, A.; Davis, D. G. J . Magn. Reson.

1985, 63, 207-213.

2894 Organometallics, Vol. 20, No. 13, 2001

Go¨ttker-Schnetmann et al.

F igu r e 5. Molecular structure of compound 10c. Selected

bond lengths (Å) and angles (deg): N1-C3 1.391(7), C3-C

81.386(7), C8-C9 1.523(7), C9-C12 1.571(7), C12-N1

1.485(6), C12-C13 1.497(7), C13-C14 1.325(7), C14-C15

1.473(8), C15-C16 1.361(7), C16-C12 1.526(7); C2-N1-

C12 119.1(5), C2-N1-C3 119.3(5), C3-N1-C12 107.7(4),

N1-C3-C8 110.7(5), C3-C8-C9 108.9(5), C8-C9-C12

100.6(4), C9-C12-C13 115.6(5), C12-C13-C14 108.8(5),

C13-C14-C15 112.6(5), C14-C15-C16 105.7(5), C15-

C16-C12 110.5(5), C16-C12-C13 102.2(5); C2-N1-C3-

C8 159.3(4), N1-C3-C8-C9 1.3(6), C3-C8-C9-C12

19.7(5), C8-C9-C12-N1 29.4(5), C9-C12-N1-C2

170.6(5), C8-C9-C12-C13 152.9(4), C9-C12-C13-C14

124.7(5), C12-C13-C14-C15 2.1(7), C13-C14-C15-C16

2.4(7), C14-C15-C16-C12 1.6(6), C16-C12-C9-C8

89.3(5). R(N1, C3, C8, C9, C12/ C12, C13, C14, C15, C16)

) 91.5.

F igu r e 4. Molecular structure of compound 8a . Selected

bond lengths (Å) and angles (deg): W-C6 2.254(2), O61-

C6 1.335(3), C6-C7 1.446(4), C7-C10 1.376(4), C10-C11

1.408(4), C11-C12 1.368(4), C12-N13 1.369(3); W-C6-

O61 124.7(1), O61-C6-C7 107.0(2), W-C6-C7 127.3(1),

C6-C7-C8 118.8(2), C6-C7-C10 121.5(2), C7-C10-C11

124.7(2), C10-C11-C12

126.7(2), C11-C12-N13

122.6(2); O61-C6-C7-C10 164.3(2), W-C6-C7-C10

26.7(3), W-C6-C7-C8 153.9(1), C6-C7-C10-C11

177.3(2), C6-C7-C8-C9 101.9(3), C7-C10-C11-C12

179.1(2), C10-C11-C12-N13 179.9(2).

Sch em e 4. Sp ir o-F u sed Vin ylcyclop en ta d ien es 10

by π-Cycliza tion of th e 1-Meta lla -1,3,5-h exa tr ien e

Moiety of Com p ou n d s 8 Accor d in g to Ref 23

1:1 mixture of 1,2-dimethylquinolinium iodide (10a ) and

(1-alkynyl)carbene tungsten compound 1a was added

aqueous NaOH and then diethyl ether while vigorously

stirring at 20 °C. After 1 min the mixture was cooled to

-40 °C to give crystals of an analytically clean sample

1

of compound 14a . It was shown by H and ¹³C NMR

spectra in CD₂Cl₂at -40 °C, as well as by (¹H,¹³C)-

GHSQC, (¹H,¹³C)GHMBC, and ROESY experiments,

that only one isomer, namely, (3Z,5E)-6-amino-1-

metalla-1,3,5,7-octatetraene (14a ) was present in solu-

tion. If this sample was allowed to warm to 30 °C while

following the reaction by NMR spectra, a smooth

conversion into the spiro-fused cyclopentadiene 16a and

hexacarbonyltungsten could be observed within 6 h

(Scheme 5).

Spectroscopic features most characteristic of com-

pounds 16 are the signals of the spiro carbon atom at δ

75.0 (16a ) and 75.2 (16b) (shifted by ca. 12 ppm to

higher field compared to the spiro-fused indolines 6a ,c)

as well as proton signals of an AB system in the

N-heterocyclic ring [³J (¹H,¹H) ) 9.6 Hz (16a ) and 10.0

(16b ), respectively] and an AB system of the cyclo-

pentadiene ring [⁴J (¹H,¹H) ) 1.7 Hz (16a ) and 1.8 Hz

(16b), respectively].

Further structural information could be provided by

a crystal structure analysis of compound 16b (Figure 6).

Compound 16b exhibits two sets of orthogonal π-sys-

tems [R(C10,C11,C12,C13,C14/C10,N1,C2,C7,C8,C9) )

90.5°] defined by an almost planar cyclopentadiene

ring [C14-C10-C11-C12 3.9(2)°, C10-C11-C12-C13

2.8(2)°, C11-C12-C13-C14 0.3(2)°, C11-C10-C14-

C13 3.7(2)°] and the slightly puckered 1,2-dihydropyri-

dine ring [C10-N1-C2-C3 171.6(1)°, C10-N1-C2-

C7 9.4(2)°, C2-C7-C8-C9 3.1(2)°, C7-C8-C9-C10

0.6(2)°, C2-N1-C10-C9 12.1(2)°]. A similar situation

is observed in compound 17d (Figure 7), as the angle

between the cyclopentadiene and the 1,4-dihydropyri-

of their conjugated 1-metalla-1,3,5-hexatriene unit to

spiro-fused vinylcyclopentadienes 10a -d (Scheme 4).

This transformation was shown to require catalysis by

rhodium.²³A skeletal rearrangement of the type shown

in Scheme 1 was not observed under these conditions.

Single crystals of compound 10c suitable for a crystal

structure analysis were obtained by crystallization from

acetonitrile at 0 °C.

Mich a el Ad d ition of exo-Meth ylen e Dih yd r op yr i-

d in es 12a ,b a n d 13c-e. The reaction of (1-alkynyl)-

carbene complex 1a with 2-methylene-1,2-dihydro-

pyridines 12a ,b and 4-methylene-1,4-dihydropyridines

13c-e, respectively (both of which were generated

in situ by deprotonation of the respective pyridinium

salts 10a ,b and 11c-e with triethylamine), yielded

spiro-fused cyclopentadienes 16 and 17 in 68-74%

yields. The latter compounds were generated by π-cy-

clization from (very thermolabile) 1-tungsta-1,3,5,7-

octatetraene precursors 14 and 15, obtained by Michael

addition of methylene dihydropyridines 12 and 13 to the

(1-alkynyl)carbene complex 1a (Scheme 5). Formation

of cross-conjugated products by metathesis of dihydro-

pyridines 12 and 13 and (1-alkynyl)carbene complex 1a

was excluded on the basis that dCH₂signals were not

observed in the DEPT spectra (-40 °C) of the reaction

mixtures.

Other than compounds 15, which could not be isolated

analytically pure, compound 14a was readily obtained

clean by an elaborate protocol, by which to a (solid)

Spiro-Fused Cyclopentadienes

Organometallics, Vol. 20, No. 13, 2001 2895

Sch em e 5. Sp ir o-F u sed Cyclop en ta d ien es 16 a n d 17 via Mich a el-typ e Ad d ition of exo-Meth ylen e

Dih yd r op yr id in es to (1-Alk yn yl)ca r ben e Com p lex 1a

dine ring was found to be R(C4, C5, C6, C7, C8/ C4, C3,

C2, N1, C14, C9) ) 90.3°.

tetrafluoroborat 11g with compound 1a under condi-

tions identical to those applied for the generation of

spiro-fused cyclopentadienes 16 and 17 or metalatetra-

ene 14a did not afford analogous products, but zwitter-

ionic pyridinium carbonylmetalates 18f,g in 51-53%

isolated yield after chromatography. Formation of com-

pounds 18 is suggested to proceed via a nucleophilic

attack of the exo-methylene carbon atom to the carbene

carbon atom to form a zwitterionic adduct, which

subsequently rearranges to a novel pyridinium carbo-

nyltungstate 18 by deprotonation/protonation and [1,2]-

migration of the pentacarbonyltungstate moiety^17,18

(Scheme 6). The E/ Z ratio of the products 18 and 18′ is

in line with the expectation considering the supposed

population of the anionic precursors E:E′ based on

gauche interactions (Scheme 6).

The ¹³C NMR signals of the spiro carbon atoms of

compounds 17 were observed at δ 56.6 (17c), 56.7 (both

17d and 17e), at higher field than in the N-substituted

spiro compounds 6 or 16. The substitution pattern of

the cyclopentadiene ring was characterized by an AB-

system with ⁴J ) 1.9 Hz (17c) and 1.5 Hz (17d ),

respectively. An AB-system was observed also for the

3

benzannelated 1,4-dihydropyridine rings with J ) 8.0

Hz (17c,d ), and an AA′BB′-system was found for the

1,4-dihydropyridine 17e.

Novel P yr id in iu m Ca r bon yltu n gsta tes. It has

been pointed out above (footnote to table in Scheme 4)

that a Michael-type 4-addition as well as a metathesis

between 4-methylene dihydropyridines 13 and (1-alkyn-

yl)carbene complex 1a was completely outrun by a

reaction not specified above, which we now identify as

resulting from the 2-addition of the methylene carbon

to the carbene carbon.^14-16Reaction of 1,4-dimethyl

pyridinium iodide 11f or 1-ethyl-4-methyl pyridinium

(15) Nucleophilic 2-addition of 1-aza-1,3-butadienes to (1-alkynyl)-

carbene complexes and subsequent [1,2]-migration of the metal has

been reported by: (a) Barluenga, J .; Toma´s, M.; Rubio, E.; Lo´pez-

Pelegr´ın, J . A.; Garc´ıa-Granda, S.; Pertierra, P. J . Am. Chem. Soc.

1996, 118, 695-696. (b) Aumann, R.; Fro¨hlich, R.; Zippel, F. Organo-

metallics 1997, 16, 2571-2580. (c) Aumann, R.; Yu, Z.; Fro¨hlich, R. J .

Organomet Chem. 1997, 549, 311-318. (d) Barluenga, J .; To´mas, M.;

Rubio, E.; Lo´pez-Pelegr´ın, J . A.; Garc´ıa-Granda, S.; Pe´rez Priede, M.

J . Am. Chem. Soc. 1999, 121, 3065-3071.

(16) Nucleophilic 2-addition of uncharged carbon nucleophiles to

(1-alkynyl)carbene complexes has been previously proposed by: (a)

See ref 15d. (b) Aumann, R.; Heinen, H.; Hinterding, P.; Stra¨ter, N.;

Krebs, B. Chem. Ber. 1991, 124, 1229-1236. (c) Fischer, H.; Meissner,

T.; Hofmann, J . J . Organomet. Chem. 1990, 397, 41-49. (d) Wu,

H.-P.; Aumann, R.; Fro¨hlich, R.; Saarenketo, P. Chem. Eur. J . 2001,

7, 700-710.

(14) Nucleophilic 1,2-addition by the nitrogen of 1,4-dihydro-

pyridines to Fischer carbene complexes has been reported by: (a)

Cohen, F.; Goumont, R.; Rudler, H. J . Organomet. Chem. 1992, 431,

C6-C10. (b) Rudler, H.; Audouin, M.; Parlier, A.; Mart´ın-Vaca, B.;

Goumont, R.; Durand-Re´ville, T.; Vaissermann, J . J . Am. Chem. Soc.

1996, 118, 12045-12058. (c) Mart´ın-Vaca, B.; Rudler, H.; Audouin,

M.; Nicolas, M.; Durand-Re´ville, M.; Vissie`re, B. J . Organomet. Chem.

1998, 567, 119-126. (d) Rudler, H.; Mart´ın-Vaca, B.; Nicolas, M.;

Vaissermann, J . Organometallics 1998, 17, 361-366.

2896 Organometallics, Vol. 20, No. 13, 2001

Go¨ttker-Schnetmann et al.

F igu r e 6. Molecular structure of spiro fused vinyl cyclo-

pentadiene 16b. Selected bond lengths (Å) and angles

(deg): C10-C11 1.519 (2), C11-C12 1.342(2), C12-C13

1.475(2), C13-C14 1.337(2), C14-C10 1.530(2), N1-C2

1.379(2), C2-C7 1.408(2), C7-C8 1.447(2), C8-C9 1.320(2),

C9-C10 1.506(2), C10-N1 1.463(2), C12-C121 1.475(2);

C2-N1-C18 120.3(1), C10-N1-C18 115.3(1), C2-N1-

C10 123.6(1), N1-C10-C9 111.8(1), N1-C10-C11 114.4(1),

N1-C10-C14 112.2(2), C9-C10-C11 108.6(1), C12-C11-

C10 110.8(1), C11-C12-C13 109.1(1), C12-C13-C14

108.6 (1), C13-C14-C10 111.0(1), C11-C10-C14 100.4(1),

N1-C2-C7 120.4(1), C2-C7-C8 118.2(1), C9-C8-C7

121.7(1), C8-C9-C10 123.3(1); C10-N1-C2-C3 171.6(1),

C10-N1-C2-C7 9.4(2), C2-C7-C8-C9 3.1(2), C7-C8-

C9-C10 0.6(2), C2-N1-C10-C9 12.1(2), C2-N1-C10-

C14 134.6(1), C8-C9-C10-C11 119.5(2), C8-C9-C10-

C14 132.1(2), N1-C10-C11-C12 124.2(1), C9-C10-C11-

C12 110.1(1), C14-C10-C11-C12 3.9(2), C10-C11-C12-

C13 2.8(2), C11-C12-C13-C14 0.3(2), N1-C10-C14-

C13 125.6(1), C9-C10-C14-C13 110.1(1), C11-C10-

C14-C13 3.7(2).

F igu r e 7. Molecular structure of spiro vinyl cyclopenta-

diene 17d . Selected bond lengths (Å) and angles (deg): N1-

C2 1.380(5), C2-C3 1.317(6), C3-C4 1.508(5), C4-C9

1.517(5), C9-C14 1.414(5), C4-C5 1.527(5), C5-C6 1.339(5),

C6-C7 1.479(5), C6-O17 1.352(4), C7-C8 1.344(5), C8-

C4 1.510(5); C2-N1-C14 119.0(3), C2-N1-C15 117.5(3),

C14-N1-C15 123.4(3), C3-C2-N1 124.8(4), C2-C3-C4

123.1(3), C3-C4-C9 110.2(3), C14-C9-C4 122.6(3), C9-

C14-N1 120.1(3), C6-C5-C4 111.5(3), C5-C6-C7 108.0(3),

C8-C7-C6 108.8(3), C7-C8-C4 111.3(3); C2-C3-C4-

C5 119.8(4), C2-C3-C4-C8 132.2(4), C3-C4-C5-C6

107.4(3), C3-C4-C8-C7 106.8(4), C9-C4-C5-C6 129.6(3),

C9-C4-C8-C7 128.8(3).

Sch em e 6. Zw itter ion ic P yr id in iu m

Ca r bon ylm eta la tes 18f,g by 2-Ad d ition of

Meth ylen e Dih yd r op yr id in es 13e,f

The fact that exo-methylene dihydropyridines 13f,g

exhibit a much higher tendency to form 2-adducts than

the corresponding exo-methylene (exo-prop-2-enylidene)-

indolines 2a -d seems to be controlled by the nucleo-

philicity of the corresponding methylene carbon atoms.

It appears that “harder” and also sterically less hindered

carbon nucleophiles would rather undergo a 2-addition

to (1-alkynyl)carbene complexes 1 than a 4-addition. Up

to date, only a few examples of a 1,2-addition of neutral

carbon nucleophiles to (1-alkynyl)carbene complexes

have been reported.¹⁶Examples for the addition of

anionic carbon nucleophiles are more common.^17a,b,d,e,18

Compounds 18f,g/18′f,g are stable in solution at 300

K for several hours. Their structures have been eluci-

dated by spectroscopic techniques and a crystal struc-

1

ture analysis (Figure 8). The H and ¹³C NMR spectra

in C₆D₆showed two sets of signals in a ratio of ca. 3:2

assigned to E/ Z stereoisomers (Scheme 6). In the ¹H

(17) [1,2]-Migration of the metal has been previously reported by:

(a) Fischer, H.; Meisner, T.; Hofmann, J . Chem. Ber. 1990, 123, 1799-

1804. (b) Do¨tz, K. H.; Christoffers, C.; Knochel, P. J . Organomet. Chem.

1995, 489, C84-C86. (c) Barluenga, J .; Toma´s, M.; Ballesteros, A.;

Santamar´ıa, J .; Carbajo, R. J .; Lo´pez-Ortiz, F.; Garc´ıa-Granda, S.;

Pertierra, P. Chem. Eur. J . 1996, 2, 88-97. (d) Iwasawa, N.; Ochiai,

T.; Maeyama, K. Organometallics 1997, 16, 5137-5139. (e) Iwasawa,

N.; Ochiai, T.; Maeyama, K. J . Org. Chem. 1998, 63, 3164-3165. (f)

Barluenga, J .; Rubio, E.; Lo´pez-Pelegr´ın, J . A.; To´mas, M. Angew.

Chem. 1999, 111, 1163-1165; Angew. Chem., Int. Ed. 1999, 38, 1091-

1093. (g) Go´mez-Gallego, M.; Manchen˜o, M. J .; Ram´ırez, P.; Pin˜ar, C.;

Sierra, M. A. Tetrahedron 2000, 56, 4893-4905. And see ref 15.

(18) [1,3]-Migration of the metal is another reaction pathway, which

was described by: (a) Barluenga, J .; Trabanco, A. A.; Flo´rez, J .; Garc´ıa-

Granda, S.; Llorca, M.-A. J . Am. Chem. Soc. 1998, 120, 12129-12130.

(b) Caro, B.; Le Poul, P.; Robin-Le Guen, F.; Se´ne´chal-Tocquer, M.-C.;

Saillard, J .-Y.; Kahlal, S.; Ouahab, L.; Gohlen, S. Eur. J . Org. Chem.

2000, 577-581.

NMR spectra at 300 K only two pyridinium protons CH-

N⁺(R)dCH were detected for the major isomer 18f at δ

5.77 (5.85 for the minor isomer 18′f) [18g, δ 5.94; 18′g,

5.98], whereas the other pyridinium protons remained

unobserved due to dynamic line-broadening. The proton

PhCH in each isomer 18f,g/18′f,g appears as a three-

line pattern with a line intensity of ca. 1:12:1 at δ 7.59

Spiro-Fused Cyclopentadienes

Organometallics, Vol. 20, No. 13, 2001 2897

were found to be dependent on the reaction conditions

as well as on the nucleophilicity of the carbon nucleo-

philes. Addition of “soft” 2-methyleneindoline 2a gave

conjugated metallahexatrienes 4a ,c and cross-conju-

gated metallahexatrienes 3a ,c by 1,4-addition and me-

tathesis, respectively. Vinylogous compounds, like 2-pro-

penylideneindolines 2b-d afforded cross-conjugated

metallaoctatetraenes 8 and 9 resulting from metathesis

of the exo-propenylidene moiety at the 1,2- and the 3,4-

double bond position, respectively. 2-Methylene-1,2-

dihydropyridines 12a ,b and 4-methylene-1,4-dihydro-

pyridines 13c-e yielded conjugated metallaoctatetraenes

14 and 15 by 4-addition, from which finally spiro com-

pounds 16 and 17 could be obtained. 4-Methylene-1,4-

dihydropyridines 13f,g, on the other hand, afforded no

4-addition products but novel pyridinium carbonylmeta-

lates 18 by 2-addition. Thus addition of “hard” and ster-

ically less crowded nucleophiles was found to provide

an up to date rarely investigated access to the formation

of carbiminium carbonyltungstates by 2-addition.

F igu r e 8. Molecular structure of pyridinium carbonyl

tungstate 18f. Selected bond lengths (Å) and angles (deg):

W1-C6 2.306(4), C6-C7 1.338(6), C7-C8 1.483(5), C6-

C14 1.464(6), C14-C18 1.372(6), C14-O15 1.347(5), C18-

C19 1.407(5), C19-C20 1.418(5), C19-C24 1.405(6), C20-

C21 1.354(6), C21-N22 1.344(5), N22-C23 1.351(5), C23-

C24 1.351(6), C24-C19 1.405(6), N22-C25 1.474(5); W1-

C6-C7 126.0(3), W1-C6-C14 110.5(3), C6-C7-C8

130.8(4), C6-C14-O15 120.8(3), C6-C14-C18 120.6(4),

C14-C18-C19 131.5(4), C21-N22-C25 122.0(4), C21-

N22-C23 119.2(4), C23-N22-C25 118.8(4); W1-C6-C7-

C8 176.8(3), W1-C6-C14-C18 83.9(3), W1-C6-C14-

O15 91.9(3), C6-C14-C18-C19 175.8(3), C7-C6-C14-

C18 89.9(5), C14-C18-C19-C20 2.2(7).

Exp er im en ta l Section

NMR: Bruker AM 360, Bruker AMX 400, and Varian U 600.

All thermally stable compounds were routinely analyzed by

¹H and ¹³C NMR experiments including (¹H,¹H)COSY, (¹H,¹³C)-

GHSQC, and (¹H,¹³C)GHMBC experiments at a Bruker AMX

400 instrument. NOE and ROESY experiments were per-

formed at a Varian U 600 instrument. Low-temperature

experiments were performed either at the Bruker AM 360 or

Varian U 600. IR: FT-IR BIO-RAD DIGILAB DIVISION FTS-

45. MS: FINNIGAN MAT8200. MALDI-TOF: Lazarus III DE

provided by Dr. H. Luftmann, Organisch-Chemisches Institut

der Universita¨t Mu¨nster. Elemental analyses: HERAEUS

CHN-O Rapid. Column chromatography: ICN Alumina N

activity IV (10% H₂O) and Merck silica gel 60F. Flash

chromatography was performed under an argon pressure of

1.2 bar within ca. 15 min for each compound. Fast chromato-

graphic separation was performed by use of reduced pressure

(250 mbar) at the end of the column within 5 min. TLC: Merck

silica gel 60F₂₅₄. R_fvalues are based on TLC tests and are

uncorrected. Melting points are uncorrected. All reactions were

performed under argon. CH₂Cl₂(p.a. quality), diethyl ether,

n-pentane, C₆D₆, toluene-d₈, CDCl₃, and CD₂Cl₂were used as

purchased and not dried prior to use. Compounds 1 were

prepared according to refs 2 and 21, and compounds 2b-d

according to ref 12. Compounds 8 and 9 were produced in

virtual quantitative yield by adding 0.95 equiv of methyl iodide

or triethyl oxonium tetrafluoroborate to solutions of lepidine,

chinaldine, or the respective alkyl pyridine in CH₂Cl₂, refluxing

for several hours, and removal of the solvent and the remain-

ing pyridines together with n-pentane. 1,3,3-Trimethyl-2-

methylene-indoline 2a was used as purchased from Fluka.

P en ta ca r bon yl[1-eth oxy-3-p h en yl-4-(1,3,3-tr im eth ylin -

d olin -2-ylid en e)b u t -2-en ylid en e]t u n gst en (4a ), P en t a -

ca r b on yl[1-et h oxy-3-p h en yl-2-(1,3,3-t r im et h yl-in d olin -

2-ylid en e)b u t -3-en ylid en e]t u n gst en (3a ), 3-P h en yl-2-

(1,3,3-tr im eth ylin d olin -2-ylid en e)bu t-3-en a l (7a ), Tetr a -

ca r bon yl[1-eth oxy-3-p h en yl-2-(1,3,3-tr im eth ylin d olin -2-

ylid en e)b u t -3-en ylid en e]t u n gst en (5a ), a n d Sp ir o[2-

eth oxy-4-p h en ylcyclop en ta -2,4-d ien e-1,2′-N-m eth yl-3′,3′-

d im eth ylin d olin e] (6a ). To pentacarbonyl(1-ethoxy-3-phenyl-

propyn-1-ylidene)tungsten (1a ) (482 mg, 1.0 mmol) in a 4 mL

screw-top vessel was added a solution of 1,3,3-trimethyl-2-

methyleneindoline 2a (173 mg, 1.0 mmol) in diethyl ether.

Compound 1a was consumed at 20 °C after stirring for 1 h

(TLC). Separation of compounds 3a and 4a was achieved by

for compound 18f (18′f: 7.50) [18g, δ 7.63; 18′g, 7.52]

resulting from ³J (¹H,¹⁸³W) ) 6.8 Hz (18f/18′f) and 6.6

Hz (18g/18′g).^{19,20 1}H NMR spectra of compounds 18f/

18′f in CD₂Cl₂at 213 K, 600 MHz, exhibit signals of

the remaining pyridinium protons with the expected

splitting pattern. Spin-saturation transfer experiments

indicated a slow chemical exchange between these

protons in each isomer, resulting from hindered rota-

tion. Additional NOE as well as GHSQC and GHMBC

experiments allowed a complete assignment of the

signals to the major and minor isomer of compounds

18f/18′f. Further structural information was provided

by a crystal structure analysis of compound 18f.

Most characteristic of the molecular structure of

compound 18f in the solid state is the perpendicular

distortion of the W1-C6-C7 unit against the plane

defined by the atoms C14-C18-C19 [dihedral angles

C7-C6-C14-C18 89.9(5)°, W1-C6-C7-C18 83.9(3)°,

and C6-C14-C18-C19 175.8(3)°]. Due to an essentially

planar arrangement of the C6-C14-C18-C19-C20

chain with dihedral angles C6-C14-C18-C19 175.8(3)°

and C14-C18-C19-C20 2.2(7)°, the positive charge is

delocalized by π-interaction, resulting in nearly equal

bond distances C24-C19 1.405(6)°, C20-C19 1.418(5)°,

and C18-C19 1.407(5)°.

Con clu sion

Three different reaction pathways were established

for reactions of exo-methylene N-heterocycles 2, 12, and

13 with (1-alkynyl)carbene tungsten complexes 1. They

comprise Michael-type 4-additions, metathetical reac-

tions, and 2-additions. The different reaction modes

(19) The natural abundance of ¹⁸³W is 14.3%. Superposition of a

doublet rising from a ³J (¹H,¹⁸³W) coupling and the singlet of the

uncoupled signal is expected to show a pseudotriplet with an intensity

ratio of 1:12:1.

(20) Compound 4b was found to exhibit the same types of satellites

rising from a ³J (¹H,¹⁸³W) coupling for the proton WdC(OEt)-CH; see

Experimental Section.

(21) Aumann, R.; Fro¨hlich, R.; Prigge, J .; Meyer, O. Organometallics

1999, 18, 1369-1380.

2898 Organometallics, Vol. 20, No. 13, 2001

Go¨ttker-Schnetmann et al.

fast chromatography on neutral alumina (activity IV) with

n-pentane/diethyl ether, 10:1, under reduced pressure. The

first colorless fraction contained small amounts of compound

6a and W(CO)₆. Compound 4a was eluted as a deep purple

fraction [340 mg, 52%, mp 112 °C dec, R_f) 0.8 on silica gel

with n-pentane/diethyl ether, 10:1]. A red-brown fraction of

compound 3a containing a small amount of compound 5a and

a colorless fraction of aldehyde 7a were finally eluted. Slow

evaporation of the solvent yielded a single crystal of compound

7a suitable for a crystal structure analysis. A pure sample of

compound 3a (282 mg, 43%, mp 97 °C, R_f) 0.6 on silica gel,

n-pentane/diethyl ether, 10:1) was obtained from the fraction

containing 3a and traces of 5a by crystallization from diethyl

ether at -40 °C. Compound 6a was generated by heating a

solution of compound 4a (327 mg, 0.50 mmol) in C₆D₆at 55

°C for 10 h after chromatography on silica gel (128 mg, 77%,

R_f) 0.9 on silica gel with n-pentane/diethyl ether, 20:1). The

same compound was also obtained from compound 3a (327 mg,

0.50 mmol) in C₆D₆at 70 °C, 60 h in a sealed NMR tube (119

mg, 72%), and it was also obtained from pentacarbonyl(1-

ethoxy-3-phenylpropyn-1-ylidene)tungsten (1a ) (482 mg, 1.0

mmol) and 1,3,3-trimethyl-2-methyleneindoline (173 mg, 1.0

mmol) in 4 mL of toluene at 80 °C, 40 h (248 mg, 75%).

parameters, R ) 0.059, wR₂) 0.146, max. residual electron

density 3.26 (-4.65) e Å^-3close to tungsten, hydrogens

calculated and refined as riding atoms.

1

3a . H NMR (400 MHz, C₆D₆, 300 K): δ 7.56 (2 H, m, o-H

Ph), 7.18 (2 H, m, m-H Ph), 7.06 (1 H, m, p-H Ph), 6.98 (1 H,

m, 10-H), 6.88 (1 H, m, 9-H), 6.71 (1 H, m, 8-H), 6.47 (1 H, m,

3

11-H), 6.18 and 5.44 (1:1 H, s each, 5-H₂), 4.52 (2 H, q, J )

7.0 Hz, OCH₂), 2.94 (3 H, s, NCH₃), 1.09 [6 H, s, br, 7-(CH₃)₂],

1.00 (3 H, t, ³J ) 7.0 Hz, OCH₂CH₃). ¹³C NMR (100 MHz, C₆D₆,

300 K): δ 270-266 (C_q, very broad, C2), 204.2 and 201.1 [C_q

each, cis- and trans-CO W(CO)₅], 176.8 (C_q, C6), 146.5 (C_q, C4),

142.8 (C_q, C11a), 141.9 (C_q, i-C Ph), 141.3 (C_q, C7a), 129.0 (CH,

m-C Ph), 128.5 (CH, C10), 128.0 (CH, p-C Ph), 127.7 (CH, o-C

Ph), 126.7 (C_q, C3), 125.9 (CH, C9), 123.0 (CH₂, C5), 122.4 (CH,

C8), 111.2 (CH, C11), 75.1 (OCH₂), 51.8 (C_q, C7), 37.2 (NCH₃),

27.3 [CH₃, 7-(CH₃)₂], 16.0 (OCH₂CH₃). IR (diffuse reflection),

cm^-1(%): 2967 (15), 2051 (74), 1955 (51), 1898 (100), 1475

(58), 1365 (47), 1120 (45), 1080 (45). IR (hexane), cm^-1(%):

2059 (20), 1975 (8), 1930 (100). MS (¹⁸⁴W, 70 eV), m/e (%): 627

(16) [M⁺- CO], 599 (6) [M⁺- 2 × CO], 571 (100) [M⁺- 3 ×

CO], 515 (26) [M⁺- 5 × CO], 486 (44), 458 (73), 427 (19), 326

(12). Anal. Calcd for C₂₈H₂₅NO₆W (655.4): C, 51.32; H, 3.84;

N, 2.14. Found: C, 51.05; H, 3.79, N 2.33.

1

4a . H NMR (600 MHz, 253 K, CDCl₃): δ 7.44 (3H, m, m-

and p-H Ph), 7.38 (1 H, s, 3-H), 7.36 (2 H, m, o-H Ph), 7.30 (1

H, m, 8-H), 7.25 (1 H, m, 10-H), 7.11 (1 H, m, 9-H), 6.71 (1 H,

3

m, 11-H), 6.14 (1 H, s, 5-H), 4.71 (2 H, q, J ) 7.0 Hz, OCH₂-

CH₃), 2.45 (3 H, s, NCH₃), 1.53 [6 H, s, C(CH₃)₂], 1.47 (3 H, t,

³J ) 7.0 Hz, OCH₂CH₃). ¹³C NMR (600 MHz, 253 K, CDCl₃):

δ 280.2 (C_q, WdC), 204.7 and 199.1 [Cq each,1:4, trans- und

cis-CO W(CO)₅], 171.4 (C_q, C6), 147.3 and 145.1 (C_qeach, i-C

Ph and C4), 143.9 (C_q, C11a), 138.2 (C_q, C7a), 138.1 (CH, C3),

129.6, 129.3, and 128.8 (CH each, o-, m-, and p-C Ph), 128.1

(CH, C10), 123.0 (CH, C8), 122.1 (CH, C9), 108.7 (CH, C11),

96.7 (CH, C5), 78.1 (OCH₂), 48.6 (C_q, C7), 35.4 (NCH₃), 28.2

[C(CH₃)₂], 15.9 (OCH₂CH₃). IR (diffuse reflection), cm^-1(%):

2053 (30), 1966 (6), 1907 (100), 1558 (14), 1460 (18). IR

(hexane), cm^-1(%): 2057 (27), 1932 (100). MS (¹⁸⁴W, 70 eV),

m/e (%): 599 (9) [M⁺- 2 × CO], 571 (8) [M⁺- 3 × CO], 515

(11) [M⁺- 5 × CO], 485 (13), 331 (64), 302 (100), 272 (71),

258 (25). Anal. Calcd for C₂₈H₂₅NO₆W (655.4): C, 51.32; H,

3.84; N, 2.14. Found: C, 51.47; H, 3.71; N, 2.44. X-ray crystal

structure analysis of 4a :²²formula C₂₈H₂₅NO₆W, M ) 655.34,

red crystal 0.40 × 0.20 × 0.10 mm, a ) 10.104(1) Å, b )

11.408(1) Å, c ) 12.796(1) Å, R ) 99.66(1)°, â ) 93.66(1)°, γ )

114.62(1)°, V ) 1307.0(3) Å³, F_calc) 1.665 g cm^-3, µ ) 44.61

cm^-1, empirical absorption correction via ψ scan data (0.269

e T e 0.664), Z ) 2, triclinic, space group P1h (No. 2), λ )

0.71073 Å, T ) 223 K, ω/2θ scans, 5550 reflections collected

1

6a . H NMR (400 MHz, C₆D₆, 300 K): δ 7.47 (2 H, m, o-H

Ph), 7.21 (2 H, m, m-H Ph), 7.16 (1 H, m, 6′-H), 7.13 (1 H, m,

p-H Ph), 6.98 (1 H, m, 4′-H), 6.82 (1 H, m, 5′-H), 6.47 (1 H, m,

7′-H), 6.03 (1 H, d, ⁴J ) 1.7 Hz, 5-H), 5.22 (1 H, d, ⁴J ) 1.7 Hz,

3-H), 3.42 (2 H, m, OCH₂), 2.55 (3 H, s, NCH₃), 1.41 and 1.35

[3:3 H, s each, 3′-(CH₃)₂], 0.83 (3 H, t, ³J ) 7.2 Hz, OCH₂CH₃).

¹³C NMR (100 MHz, C₆D₆, 300 K): δ 168.7 (C_q, C2), 152.3 (C_q,

C7′a), 145.5 (C_q, C4), 140.1 (C_q, C3′a), 135.8 (C_q, i-C Ph),128.7

(CH, m-C Ph), 128.3 (CH, C6′), 127.7 (CH, p-C Ph), 126.2 (CH,

o-C Ph), 121.0 (CH, C4′), 118.6 (CH, C5), 118.0 (CH, C5′), 107.0

(CH, C7′), 96.8 (CH, C3), 87.6 (C_q, C1), 64.8 (OCH₂), 47.3 (C_q,

C3′), 30.5 (NCH₃), 28.8 and 22.1 [CH₃each, 3′-(CH₃)₂], 14.3

(OCH₂CH₃). IR (diffuse reflection), cm^-1(%): 2976 (18), 1620

(70), 1603 (58), 1484 (93), 1297 (41), 740 (100). MS (70 eV),

m/e (%): 331 (84) [M⁺], 316 (43), 302 (100), 272 (67), 258 (21).

Anal. Calcd for C₂₃H₂₅NO (331.4): C, 83.34; H, 7.60, N 4.23.

Found: C, 83.10; H, 7.73, N 4.36. X-ray crystal structure

analysis of 6a :²²formula C₂₃H₂₅NO, M ) 331.44, colorless

crystal 1.00 × 0.50 × 0.30 mm, a ) 8.443(1) Å, b ) 9.047(1)

Å, c ) 13.215(2) Å, R ) 101.79(1)°, â ) 106.43(1)°, γ )

((h, -k, (l), [(sin θ)/λ] ) 0.62 Å^-1, 5275 independent (R_int

)

0.052) and 4665 observed reflections [I g 2σ(I)], 329 refined

(22) X-ray structure analysis: Data sets were collected with Enraf-

Nonius CAD4, Nonius MACH3, and KappaCCD diffractometers, the

later two equipped with a Nonius FR591 rotating anode generator.

Programs used: data collection EXPRESS (Nonius B.V., 1994) and

COLLECT (Nonius B.V., 1998), data reduction MolEN (K. Fair, Enraf-

Nonius B.V., 1990) and Denzo-SMN (Otwinowski, Z.; Minor, W.

Methods Enzymol. 1997, 276, 307-326), absorption correction for CCD

data SORTAV (Blessing, R. H. Acta Crystallogr. 1995, A51, 33-37;

Blessing, R. H. J . Appl. Crystallogr. 1997, 30, 421-426), structure

solution SHELXS-86 and SHELXS-97 (Sheldrick, G. M. Acta Crystal-

logr. 1990, A46, 467-473), structure refinement SHELXL-93 and

SHELXL-97 (Sheldrick, G. M. Universita¨t Go¨ttingen, 1997), graphics

DIAMOND (Brandenburg, K. Universita¨t Bonn, 1997).

94.18(1)°, V ) 938.5(2) Å³, F_calc) 1.173 g cm^-3, µ ) 5.46 cm^-1

,

empirical absorption correction via ψ scan data (0.925 e C e

0.999), Z ) 2, triclinic, space group P1h (No. 2), λ ) 1.54178 Å,

T ) 223 K, ω/2θ scans, 3993 reflections collected ((h, (k, +l),

[(sin θ)/λ] ) 0.62 Å^-1, 3823 independent (R_int) 0.018) and 3643

observed reflections [I g 2σ(I)], 231 refined parameters, R )

(23) Go¨ttker-Schnetmann, I.; Aumann, R.; Bergander, K. Organo-

metallics, in press.

Spiro-Fused Cyclopentadienes

Organometallics, Vol. 20, No. 13, 2001 2899

0.049, wR₂) 0.141, max. residual electron density 0.30 (-0.23)

5-H), 4.51 and 4.37 (1:1 H, m each, OCH₂), 2.59 (3 H, s, NCH₃),

1.49 and 1.39 [3:3 H, s each, 7-(CH₃)₂], 0.83 (3 H, t, J ) 7.1

3

e Å^-3, hydrogens calculated and refined as riding atoms.

Hz, OCH₂CH₃), 0.28 [9 H, s, Si(CH₃)₃]. ¹³C NMR (90 MHz,

CDCl₃, 243 K): δ 273.1 (C_q, C2), 204.5 and 199.1 [C_qeach,

trans- and cis-CO W(CO)₅]_,169.1 (C_q, C6), 153.6 (C_q, C4), 146.0

(C_q, C11a), 144.1 (CH, C3), 138.4 (C_q, C7a); 128.3, 123.1 and

122.3 (CH each, C8-C10), 108.6 (CH, C11), 99.3 (CH, C5), 78.3

(OCH₂), 47.9 (C_q, C7), 35.1 (NCH₃), 26.4 [CH₃, 7-(CH₃)₂], 15.4

(OCH₂CH₃), -1.3 [CH₃, Si(CH₃)₃]. IR (diffuse reflection), cm^-1

(%): 2961 (18), 2053 (68), 1966 (33), 1915 (100), 1565 (26), 1454

(44). IR (hexane), cm^-1(%): 2057 (23), 1970 (6), 1931 (100).

5a . ¹H NMR (400 MHz, C₆D₆, 300 K): δ 7.32, 7.1-6.94, 6.88,

and 6.10 (2:2:4:1 H; s br, s br, m, m; Ph and 8-H-11-H), 4.39

and 4.15 (1:1 H, s each, 5-H₂), 4.32 (2 H, m, OCH₂), 2.63 (3 H,

s, NCH₃), 1.55 and 1.44 [3:3 H, s each, 7-(CH₃)₂], 1.21 (3 H, t,

³J ) 7.2 Hz, OCH₂CH₃). ¹³C NMR (100 MHz, C₆D₆, 300 K): δ

269.6 (C_q, C2); 218.2, 213.6, 208.6, and 208.3 [C_qeach, W(CO)₄],

157.7 (C_q, C6), 143.5 (C_q, C7a), 140.9 and 140.8 (C_qeach, C11a

and i-C Ph); 129.6-128.5 (br), 128.0 and 126.3-125.2 (br) (CH

each, Ph); 127.6, 124.5, 121.7, and 109.9 (CH each, C8-C11),

117.0 (C_q, C3), 95.6 (C_q, C4), 75.7 (OCH₂), 64.9 (CH₂, C5), 50.5

(C_q, C7), 33.0 (NCH₃), 26.8 and 23.3 [CH₃each, 7-(CH₃)₂], 14.8

(OCH₂CH₃). IR (diffuse reflection), cm^-1(%): 2009 (69), 1976

(8), 1905 (100), 1855 (73), 1478 (46), 1367 (23), 1285 (19). IR

(hexane), cm^-1(%): 2019 (72), 1983 (69), 1935 (100), 1891 (72).

X-ray crystal structure analysis of 7a :²²formula C₂₁H₂₁NO,

M ) 303.39, yellow crystal 0.60 × 0.60 × 0.40 mm, a )

11.641(1) Å, b ) 8.886(1) Å, c ) 16.540(1) Å, â ) 103.09(1)°, V

) 1666.5(3) Å³, F_calc) 1.209 g cm^-3, µ ) 0.74 cm^-1, empirical

absorption correction via ψ scan data (0.957 e T e 0.971), Z

) 4, monoclinic, space group P2₁/n (No. 14), λ ) 0.71073 Å, T

) 223 K, ω/2θ scans, 3536 reflections collected (-h, -k, (l),

[(sin θ)/λ] ) 0.62 Å^-1, 3369 independent (R_int) 0.035) and 2596

observed reflections [I g 2σ(I)], 211 refined parameters, R )

0.066, wR₂) 0.196, max. residual electron density 0.38 (-0.43)

e Å^-3, hydrogens calculated and refined as riding atoms.

P en t a ca r b on yl[1-et h oxy-3-t r im et h ylsilyl-4-(1,3,3-t r i-

m eth ylin d olin -2-ylid en e)bu t-2-en ylid en e]tu n gsten (4b)

a n d Spir o[2-eth oxy-4-tr im eth ylsilylcyclop en ta -2,4-dien e-

1,2′-N-m et h yl-3′,3′-d im et h ylin d olin e] (6b ). To pentacar-

bonyl(1-ethoxy-3-trimethylsilylpropyn-1-ylidene)tungsten (1b)

(478 mg, 1.00 mmol) in a 4 mL screw-top vessel was added

1,3,3-trimethyl-2-methyleneindoline (2a ) (173 mg, 1.00 mmol)

in 4 mL of toluene. Compound 1c was consumed after stirring

for 30 min at 20 °C (TLC). Additional stirring for 12 h at 50

°C, removal of the solvent, and chromatography on neutral

alumina (activity IV) yielded compound 6b as a colorless oil

(254 mg,78%, R_f) 0.8 in n-pentane/diethyl ether, 20:1). A

sample of compound 4b containing an impurity of compound

6b and W(CO)₆was generated from pentacarbonyl(1-ethoxy-

3-trimethylsilylpropyn-1-ylidene)tungsten (1b) (478 mg, 1.00

mmol) and 1,3,3-trimethyl-2-methyleneindoline (2a ) (173 mg,

1.00 mmol) in 4 mL of diethyl ether after stirring 30 min at

20 °C and fast chromatography on neutral alumina (activity

IV) (482 mg, ca. 74%, R_f) 0.7 with n-pentane/diethyl ether,

20:1). This sample was shown by NMR monitoring to produce

compound 6b after 6 h at 30 °C in a smooth reaction (260 mg,

79%).

6b. ¹H NMR (400 MHz, C₆D₆, 300 K): δ 7.22 (1 H, m, 6′-H),

6.94 (1 H, m, 4′-H), 6.74 (1 H, m, 5′-H), 6.45 (1 H, m, 7′H),

6.02 (1 H, d, ⁴J ) 1.7 Hz, 5-H), 4.92 (1 H, d, ⁴J ) 1.7 Hz, 3-H),

3.40 (2 H, m OCH₂), 2.52 (3 H, s, NCH₃), 1.37 and 1.32 [3:3 H,

3

s each, 3′-(CH₃)₂], 0.84 (3 H, t, J ) 7.2 Hz, OCH₂CH₃), 0.20

[9 H, s, Si(CH₃)₃]. ¹³C NMR (100 MHz, C₆D₆, 300 K):

δ

167.8 (C_q, C2), 152.3 (C_q, C7′a), 148.0 (C_q, C4), 140.1 (C_q, C3′a),

135.7 (CH, C5), 127.6 (CH, C6′), 120.9 (CH, C4′), 117.8 (CH,

C5′), 107.0 (CH, C7′), 98.9 (CH, C3), 87.9 (C_q, C1), 64.6 (OCH₂),

46.7 (C_q, C3′), 30.5 (NCH₃), 28.7 and 22.3 [3′-(CH₃)₂], 14.4

(OCH₂CH₃), -1.5 [Si(CH₃)₃]. IR (diffuse reflection), cm^-1(%):

2953 (43), 2802 (10), 1604 (81), 1484 (89), 1312 (50), 1247 (64),

1085 (71), 836 (100). MS (70 eV), m/e (%): 327 (37) [M⁺], 312

(16), 298 (80), 283 (81), 268 (32), 210 (16), 182 (16). Anal. Calcd

for C₂₀H₂₉NOSi (327.5): C, 73.34; H, 8.92; N, 4.28. Found: C,

73.42; H, 9.00; N, 4.11.

P en ta ca r bon yl[1-eth oxy-3-cycloh ex-1-en yl-2-(1,3,3-tr i-

m eth ylin d olin -2-ylid en e)bu t-3-en ylid en e]tu n gsten (3c)

a n d Tet r a ca r b on yl[1-et h oxy-3-cycloh ex-1-en yl-2-(1,3,3-

tr im eth yl- in d olin -2-ylid en e)bu t-3-en ylid en e]tu n gsten

(5c). To pentacarbonyl[1-ethoxy-3-(cyclohex-1-enyl)propyn-1-

ylidene]tungsten (1c) (486 mg, 1.0 mmol) in a 4 mL screw-top

vessel was added 1,3,3-trimethyl-2-methyleneindoline (2a )

(173 mg, 1.0 mmol) in diethyl ether. Compound 1c was

consumed after stirring 1 h at 20 °C (TLC). After removal of

the solvent under reduced pressure (20 mbar, 20 °C) a red oil

was obtained, which was extracted carefully with 4 × 4 mL

each of n-pentane by the aid of ultrasound irradiation, then

separated by centrifugation and dried under reduced pressure

(20 mbar, then 10^-3mbar) to give compound 3c as a dark red

oil (449 mg, 68%, R_f) 0.6 on silica gel with n-pentane/diethyl

ether, 10:1). An additional 118 mg (18%) of compound 3c was

obtained from the combined organic extracts after 12 h at -40

°C. Generation of tetracarbonyl complex 5c was monitored by

NMR spectra while heating a solution of 137 mg (0.21 mmol)

of compound 3c in 0.7 mL of C₆D₆for 2 h at 50 °C in a sealed

NMR tube. The sample remained essentially unchanged after

an additional 60 h, 70 °C.

4b. ¹H NMR (360 MHz, CDCl₃, 243 K): δ 7.70 [1 H, t, 1:12:

3

1, J (¹H,¹⁸³W) ) 6.8 Hz, 3-H], 7.35 (1 H, m, 10-H), 7.31 (1 H,

m, 8-H), 7.14 (1 H, m, 10-H), 6.97 (1 H, m, 11-H), 5.47 (1 H, s,

2900 Organometallics, Vol. 20, No. 13, 2001

Go¨ttker-Schnetmann et al.

1

3c. H NMR (400 MHz, C₆D₆, 300 K): δ 7.11 (1 H, m, 10-

and 1.75 (3:3 H, s each, 13-CH₃and 14-H₃), 1.64 and 1.58 [3:3

H, s br each, 7-CH₃)₂], 1.04 (3 H, t, ³J ) 7.0 Hz, OCH₂CH₃).

¹³C NMR (150 MHz, C₆D₆, 298 K): δ 289.1 (C_q, C2), 203.1 and

H), 7.03 (1 H, m, 9-H), 6.93 (1 H, m, 8-H), 6.64 (1 H, m, 11-H),

5.99 (1 H, m br, 13-H), 5.62 and 5.16 (1:1 H, s each, 5-H₂),

4.38 (2 H, m, OCH₂), 2.98 (3 H, s, NCH₃); 2.6-2.4, 2.25-1.75,

and 1.75-1.4 (1:4:3 H, m br each, 14-H₂-17-H₂), 1.20 [6 H, s,

7-(CH₃)₂], 1.01 (3 H, t, J ) 6.9 Hz, OCH₂CH₃). ¹³C NMR (100

3

MHz, C₆D₆, 300 K): δ 269-266 (C_q, very broad, C2), 204.4 and

201.1 [C_qeach, cis- and trans-CO W(CO)₅], 177.4 (C_q, C6), 148.6

(C_q, C4), 142.7 and 141.5 (C_q, C7a and C11a), 139.8 (C_q, C12),

130.7 (CH, C13), 128.5 (CH, C10), 126.2 (C_q, br, C3), 125.9

(CH, C9), 122.2 (CH, C8), 120.1 (CH₂, C5), 111.1 (CH, C11),

74.0 (OCH₂), 51.6 (C_q, C7), 36.6 (NCH₃); 27.3-26.8, 26.0-25.8,

24.0-23.8, and 23.6-23.2 (CH₂each, br each, C14-C17), 26.5

[CH₃, 7-(CH₃)₂], 15.8 (OCH₂CH₃). IR (diffuse reflection), cm^-1

(%): 2929 (10), 2049 (19), 1900 (100), 1474 (22), 1366 (20). IR

(hexane), cm^-1(%): 2056 (15), 1927 (100). MS (¹⁸⁴W, 70 eV),

m/e (%): 631 [M⁺] (20), 605 [M⁺- CO] (23), 575 [M⁺- 2 ×

CO] (25), 517 [M⁺- 4 × CO] (54), 489 [M⁺- 5 × CO] (55),

460 (86), 458 (95), 425 (28), 378 (22), 171 (81). Anal. Calcd for

199.5 [C_qeach, cis- and trans-CO W(CO)₅], 169.2 (C_q, C6), 156.3

(CH, C4), 152.7 (C_q, C3), 143.5 (C_q, C11a), 142.6 (C_q, i-C Ph),

140.3 (C_q, C7a), 133.9 (C_q, C12), 130.8 (C_q, C13), 129.5 (CH,

o-C Ph), 127.9 (CH, m-C Ph), 127.8 (CH, C10), 126.3 (CH, p-C

Ph), 122.9 and 122.0 (CH each, C8 and C9), 108.2 (CH, C11),

97.5 (CH, C5), 77.2 (OCH₂), 47.7 (C_q, C7), 28.9 (NCH₃), 28.0

[CH₃, br, 7-(CH₃)₂], 23.0 and 21.6 (CH₃each, 13-CH₃and C14),

15.2 (OCH₂CH₃). IR (diffuse reflection), cm^-1(%): 2977 (4),

2053 (16), 1964 (9), 1906 (79), 1558 (71), 1157 (83), 1105 (100).

IR (hexane), cm^-1(%): 2057.7 (10), 1963.2 (3), 1928.8 (100),

1567.4 (14). MS (70 eV), ¹⁸⁴W m/e (%): 709 [M⁺] (1), 653 [M⁺

- 2 × CO] (3), 625 [M⁺- 3 × CO] (13), 597 [M⁺- 4 × CO]

(6), 569 [M⁺- 5 × CO] (64), 385 [M⁺- W(CO)₅] (56), 370 (79),

356 (100). Anal. Calcd for C₃₂H₃₁NO₆W (709.5): C, 54.18; H,

4.40; N, 1.97. Found: C, 54.27; H, 4.55; N, 1.97. X-ray crystal

structure analysis of 8a :²²formula C₃₂H₃₁NO₆W, M ) 709.43,

red crystal 0.25 × 0.20 × 0.10 mm, a ) 10.712(1) Å, b )

10.861(1) Å, c ) 14.835(2) Å, R ) 79.48(1)°, â ) 88.40(1)°, γ )

62.35(1)°, V ) 1499.9(2) Å³, F_calc) 1.571 g cm^-3, µ ) 38.94

cm^-1, absorption correction via SORTAV (0.443 e T e 0.697),

Z ) 2, triclinic, space group P1h (No. 2), λ ) 0.71073 Å, T )

198 K, ω and æ scans, 9934 reflections collected ((h, (k, (l),

[(sin θ)/λ] ) 0.65 Å^-1, 6811 independent (R_int) 0.029) and 6448

observed reflections [I g 2σ(I)], 367 refined parameters, R )

0.023, wR₂) 0.058, max. residual electron density 1.08 (-1.21)

e Å^-3, hydrogens calculated and refined as riding atoms.

C

₂₈H₂₉NO₆W (659.4): C, 51.00; H, 4.43; N, 2.12. Found: C,

51.05; H, 4.19; N, 2.23.

1

5c. H NMR (400 MHz, C₆D₆, 300 K): δ 7.11 (1 H, m, 10-

H), 6.98 (1 H, m, 9-H), 6.94 (1 H, m, 8-H), 6.57 (1 H, m, 11-H),

5.90 (1 H, m, 13-H), 4.36 (2 H, m, OCH₂), 4.10 and 3.77 (1:1

H, s each, 5-H₂), 3.03 (3 H, s, NCH₃), 2.6-2.4; 2.2-1.5 (1:7 H,

m br each, 14-H₂-17-H₂), 1.46 and 1.44 [3:3 H, s each, 7-(CH₃)₂],

1.26 (3 H, t, ³J ) 7.1 Hz, OCH₂CH₃). ¹³C NMR (100 MHz, C₆D₆,

300 K): δ 268.5 (C_q, C2); 216.5, 215.1, 208.6, and 206.6 [C_q

each, W(CO)₄], 158.7 (C_q, C6), 143.4 (C_q, C7a), 141.1 (C_q, C11a),

135.8 (C_q, C12), 128.3 (CH, C10), 125.7 (CH, C8), 124.6 (CH,

C9), 115.7 (C_q, C3), 104.6 (C_q, C4), 110.9 (CH, C11), 74.0

(OCH₂), 67.7 (CH₂, C5), 50.6 (C_q, C7), 32.7 (NCH₃); 26.6, 25.8,

23.2, and 22.4 (CH₂each, C14-C17), 26.5 and 23.1 [CH₃each,

7-(CH₃)₂], 14.9 (OCH₂CH₃). IR (diffuse reflection), cm^-1(%):

2008 (51), 1977 (15), 1902 (100), 1853 (57). IR (hexane), cm^-1

(%): 2015 (68), 1984 (82), 1931 (100), 1885 (70).

P en ta ca r bon yl[1-eth oxy-2-(1-p h en yl-2-m eth ylp r op -1-

e n yl)-4-(1,3,3-t r im e t h ylin d olin -2-ylid e n e )b u t -2-e n -1-

ylid en e]tu n gsten (8a ) a n d P en ta ca r bon yl[1-eth oxy-6-

m eth yl-3-ph en yl-2-(1,3,3-tr im eth ylin dolin -2-yliden e)h epta-

3,5-dien -1-yliden e]tu n gsten (9a). To pentacarbonyl[1-ethoxy-

3-phenylproyn-1-ylidene]tungsten (1a ) (482 mg, 1.00 mmol) in

a 4 mL screw-top vessel was added 1,3,3-trimethyl-2-(3-

methylbut-2-enylidene)indoline (2b) (227 mg, 1.00 mmol) in

3.5 mL of diethyl ether. The mixture was stirred for 6 h at 20

°C until compound 1a was consumed completely (TLC). The

solvent was removed by a stream of argon, and the residue

was separated by flash chromatography on silica gel with

n-pentane/diethyl ether (40:1) to afford a first purple-red

fraction containing compound 8a (342 mg, 0.48 mmol, 48%,

mp 116 °C dec, R_f) 0.8 with n-pentane/diethyl ether, 10:1)

and a second orange-red fraction containing compound 9a (235

mg, 0.33 mmol, 33%, mp 113 dec, R_f) 0.7 in n-pentane/diethyl

ether, 10:1).

1

9a . H NMR (600 MHz, C₆D₆, 298 K): δ 7.65 (2 H, o-H Ph),

3

7.19 (2 H, m, m-H Ph), 7.07 (1 H, d, J ) 11.5 Hz, 11-H), 7.00

(1 H, m, p-H Ph), 6.92 (1 H, m, 8-H), 6.86 (1 H, m, 7-H), 6.67

(2 H, m, 6-H and 12-H), 6.39 (1 H, m, 9-H), 4.37 (2 H, m,

OCH₂), 3.02 (3 H, s, NCH₃), 1.87 and 1.70 (3:3 H, s each, 13-

3

CH₃and 14-H₃), 1.18 [6 H, s br, 5-(CH₃)₂], 0.94 (3 H, t, J )

6.9 Hz, OCH₂CH₃). ¹³C NMR (150 MHz, C₆D₆, 298 K): (C2

not detected due to dynamic line broadening), δ 204.0 and

201.4 [C_qeach, cis- and trans-CO W(CO)₅], 181-178.5 (C_q, very

br, C4), 142.4 (C_q, C9a), 142.0 (C_q, i-C Ph), 141.4 (C_q, C5a),

139.9 (C_q, C13), 137.7 (C_q, br, C3), 135.1 (CH, C11), 130.9 (CH,

o-C Ph), 128.6 (C_q, br, C10) 128.3 (CH, C8), 128.2 (CH, m-C

Ph), 127.3 (CH, p-C Ph), 126.0 (CH, C7), 123.8 (CH, C12), 122.1

(CH, C6), 111.3 (CH, C9), 74.0 (OCH₂), 51.8 (C_qC5), 36.4

(NCH₃), 26.6 and 18.9 (CH₃each, 13-CH₃and C14), 26.4 [CH₃,

5-(CH₃)₂], 15.7 (OCH₂CH₃). IR (diffuse reflection), cm^-1(%):

2046 (7), 1951 (4), 1895 (100), 1473 (11), 1381 (8). IR (hexane),

cm^-1(%): 2057.7 (16), 1926.7 (100). MS (70 eV), ¹⁸⁴W m/e (%):

1

8a . H NMR (600 MHz, C₆D₆, 298 K, major isomer): δ 8.87

3

(1 H, d, J ) 13.0 Hz, 4-H), 7.37 (2 H, m, o-H Ph), 7.19 (2 H,

m, m-H Ph), 7.04 (1 H, m, p-H Ph), 6.99 (1 H, m, 10-H), 6.83

3

(2 H, m, 8-H and 9-H), 6.22 (1 H, m, 11-H), 5.80 (1 H, d, J )

13.0 Hz, 5-H), 4.64 (2 H, m, OCH₂), 2.36 (3 H, s, NCH₃), 1.93

Spiro-Fused Cyclopentadienes

Organometallics, Vol. 20, No. 13, 2001 2901

681 [M⁺- CO] (6), 653 [M⁺- 2 × CO] (16), 625 [M⁺- 3 ×

CO] (25), 569 [M⁺- 5 × CO] (25), 540 (38), 510 (44), 202 (73),

158 (100). Anal. Calcd for C₃₂H₃₁NO₆W (709.5): C, 54.18; H,

4.40; N, 1.97. Found: C, 54.33; H, 4.64; N, 1.94.

was reacted with 1,3,3-trimethyl-2-(3-phenylprop-2-enylidene)-

indoline (2d ) (275 mg, 1.00 mmol) in 3.5 mL of diethyl ether

as described above for 6 h at 20 °C. In case compound 8c did

not separate spontaneously, the mixture was cooled to -20

°C and irradiated with ultrasound in order to facilitate this

process. The solvent was removed by a stream of argon, and

compound 8c was extracted with 4 × 2 mL each of n-pentane

(653 mg, 0.86 mmol, 86%, mp 133 °C, dec, R_f) 0.8 with

n-pentane/diethyl ether, 10:1, dark red solid). Compound 8c

was transformed into the spiro-fused cyclopentadiene 10c by

a rhodium-catalyzed fragmentation.¹Single crystals of the

latter compound were obtained from acetonitrile.

P e n t a ca r b on yl[1-e t h oxy-2-(1-p h e n ylp r op -1-e n yl)-4-

(1,3,3-tr im eth ylin dolin -2-yliden e)bu t-2-en -1-yliden e]tu n g-

sten (8b). Pentacarbonyl[1-ethoxy-3-phenylproyn-1-ylidene]-

tungsten (1a ) (482 mg, 1.00 mmol) in a 4 mL screw-top vessel

was reacted with 1,3,3-trimethyl-2-(but-2-enylidene)indoline

(2c) (275 mg, 1.00 mmol) in 3.5 mL of diethyl ether as

described above for 6 h at 20 °C. If compound 8b was not

precipitated at this time, the sample was cooled to -20 °C and

irradiated with ultrasound until precipitation took place. The

solvent was removed by a stream of argon and the residue

washed with 4 × 2 mL each of n-pentane, leaving red-brown

compound 8a (573 mg, 0.82 mmol, 82%, mp 110 °C, dec, R_f)

0.8 with n-pentane/diethyl ether, 10:1, dark red-brown solid).

1

3

8c. H NMR (400 MHz, C₆D₆, 300 K): δ 9.04 (1 H, d, J )

13.0 Hz, 4-H), 7.42 (2 H, m, o-H 12-Ph), 7.24 (2 H, m, o-H 13-

Ph), 7.05 (4 H, m, m-H 12-Ph and 13-Ph), 6.97 (3 H, m, 10-H

and p-H 12-Ph and 13-Ph), 6.85 (2 H, m, 8-H and 9-H), 6.57

3

(1 H, s, 13-H), 6.22 (1 H, d, J ) 13.0 Hz, 5-H), 6.17 (1 H, m,

11-H), 4.59 (2 H, m, OCH₂), 2.24 (3 H, s, NCH₃), 1.67 [6 H, s,

3

7-(CH₃)₂], 0.94 (3 H, t, J ) 7.1 Hz, OCH₂CH₃). ¹³C NMR (100

MHz, C₆D₆, 300 K): δ 288.8 (C_q, C2), 202.9 and 199.6 [C_qeach,

cis- and trans-CO W(CO)₅], 169.4 (C_q, C6), 157.0 (CH, C4),

153.7 (C_q, C3), 143.5 (C_q, C11a), 141.0 and 140.8 (C_qeach, C12

and i-C 12-Ph), 140.4 (C_q, C7a), 138.3 (C_q, i-C 13-Ph), 131.1

(CH, C13), 129.6 and 129.5 (CH each, o-C 12-Ph and 13-Ph),

128.5 and 128.3 (CH each, m-C 12-Ph and 13-Ph), 128.1 (CH,

C10), 127.3 and 127.1 (CH each, p-C 12-Ph and 13-Ph), 123.0

and 122.0 (CH each C8 and C9), 108.2 (CH, C11), 97.6 (CH,

C5), 77.4 (OCH₂), 47.7 (C_q, C7), 28.9 (NCH₃), 28.1 [CH₃,

7-(CH₃)₂], 14.9 (OCH₂CH₃). IR (diffuse reflection), cm^-1(%):

2052 (13), 1904 (100), 1556 (25), 1150 (29), 1106 (30). IR

(hexane), cm^-1(%): 2052.6 (25), 1929.4 (100), 1563.8 (25). MS

(70 eV), ¹⁸⁴W m/e (%): 701 [M⁺- 2 × CO] (2), 673 [M⁺- 3 ×

CO] (15), 645 [M⁺- 4 × CO] (11), 613 [M⁺- 5 × CO] (100),

419 (46), 404 (43), 215 (43). Anal. Calcd for C₃₆H₃₁NO₆W

(757.6): C, 57.08; H, 4.12; N, 1.85. Found: C, 57.15; H, 4.38;

N, 1.71.

1

3

8b. H NMR (400 MHz, C₆D₆, 300 K): δ 8.96 (1 H, d, J )

13.0 Hz, 4-H), 7.38 (2 H, m, o-H Ph), 7.19 (2 H, m m-H Ph),

7.04 (1 H, m, p-H Ph), 6.99 (1 H, m, 10-H), 6.86 (2 H, m, 8-H

and 9-H), 6.23 (1 H, m, 11-H), 5.98 (1 H, d, ³J ) 13.0 Hz, 5-H),

3

5.56 (1 H, q, J ) 7.1 Hz, 13-H), 4.58 (2 H, m, OCH₂), 2.33 (3

H, s, NCH₃), 1.89 (3 H, d, ³J ) 7.1 Hz, 14-H₃), 1.66 [6 H, s,

7-(CH₃)₂], 0.98 (3 H, t, J ) 7.0 Hz, OCH₂CH₃). ¹³C NMR (100

3

10c. X-ray crystal structure analysis of 10c:²²formula

MHz, C₆D₆, 300 K): δ 289.8 (C_q, C2), 203.0 and 199.6 [C_qeach,

cis- and trans-CO W(CO)₅], 168.9 (C_q, C6), 156.6 (CH, C4),

154.3 (C_q, C3), 143.6 (C_q, C11a), 140.9 (C_q, i-C Ph), 140.4 (C_q,

C7a), 139.4 (C_q, C12), 129.1 (CH, o-C Ph), 128.1 (CH, m-C Ph),

128.0 (CH, C10), 126.8 (CH, p-C Ph), 126.3 (CH, C13), 122.8

and 122.0 (CH each, C8 and C9), 108.1 (CH, C11), 97.8 (CH,

C5), 77.3 (OCH₂), 47.6 (C_q, C7), 28.9 (NCH₃), 28.1 [CH₃,

7-(CH₃)₂], 15.4 (CH₃, C14), 14.9 (OCH₂CH₃). IR (diffuse reflec-

tion), cm^-1(%): 2053 (11), 1965 (5), 1905 (100), 1558 (29), 1154

(25), 1106 (31). IR (hexane), cm^-1(%): 2058.1 (9), 1959.5 (4),

1929.0 (100), 1567.5 (18). MS (70 eV), ¹⁸⁴W m/e (%): 695 [M⁺]

(2), 639 [M⁺- 2 × CO] (2), 611 [M⁺- 3 × CO] (11), 583 [M⁺

- 4 × CO] (4), 555 [M⁺- 5 × CO] (14), 371 [M⁺- W(CO)₅]

(31), 356 (81), 342 (100), 312 (25), 284 (19), 268 (19). Anal.

Calcd for C₃₁H₂₉NO₆W (695.4): C, 53.54; H, 4.20; N, 2.01.

Found: C, 53.29; H, 4.36; N, 1.99.

C

₃₁H₃₁NO‚C₂H₃N, M ) 474.62, yellow crystal 0.25 × 0.15 ×

0.05 mm, a ) 8.694(3) Å, b ) 16.319(4) Å, c ) 19.886(4) Å, â

) 94.15(2)°, V ) 2814.0(13) Å³, F_calc) 1.120 g cm^-3, µ ) 5.17

cm^-1, empirical absorption correction via ψ scan data (0.882

e T e 0.975), Z ) 4, monoclinic, space group P2₁/c (No. 14), λ

) 1.54178 Å, T ) 223 K, ω/2θ scans, 3988 reflections collected

((h, -k, +l), [(sin θ)/λ] ) 0.55 Å^-1, 3859 independent (R_int

)

0.069) and 1602 observed reflections [I g 2σ(I)], 330 refined

parameters, R ) 0.066, wR₂) 0.147, max. residual electron

density 0.24 (-0.21) e Å^-3, hydrogens calculated and refined

as riding atoms; due to the solvate the crystal diffracted poorly.

P en tacar bon yl[1-eth oxy-2-(1-cycloh ex-1-en yl-2-ph en yl-

eth en yl)-4-(1,3,3-tr im eth ylin d olin -2-ylid en e)bu t-2-en -1-

ylid en e]tu n gsten (8d ). Pentacarbonyl[1-ethoxy-3-(cyclohex-

1-enyl)propyn-1-ylidene]tungsten (1b) (486 mg, 1.00 mmol) in

a 4 mL screw-top vessel was reacted with 1,3,3-trimethyl-2-

(3-phenylprop-2-enylidene)indoline (2d ) (275 mg, 1.00 mmol)

in 3.5 mL of diethyl ether as described above to give compound

8d as a dark red-brown solid (627 mg, 0.82 mmol, 82%, mp

123 °C, dec, R_f) 0.9 with n-pentane/diethyl ether, 10:1).

P e n t a ca r b on yl[1-e t h oxy-2-(1,2-d ip h e n yle t h e n yl)-4-

(1,3,3-tr im eth ylin dolin -2-yliden e)bu t-2-en -1-yliden e]tu n g-

sten (8c) a n d Sp ir o[2-eth oxy-3-(1,2-d ip h en yleth en yl)-

cyclop en t a d ien e-1,2′-N-m et h yl-3′,3′-d im et h ylin d olin e]

(10c). Pentacarbonyl[1-ethoxy-3-phenylpropyne-1-ylidene]-

tungsten (1a ) (482 mg, 1.00 mmol) in a 4 mL screw-top vessel

2902 Organometallics, Vol. 20, No. 13, 2001

Go¨ttker-Schnetmann et al.

1

3

8d . H NMR (400 MHz, C₆D₆, 300 K): δ 8.89 (1 H, d, J )

13.1 Hz, 4-H), 7.48 (2 H, m, o-H Ph), 7.22 (2 H, m, m-H Ph),

7.07 (1 H, m, p-H Ph), 6.97 (1 H, m, 10-H), 6.83 (2 H, m, 8-H

and 9-H), 6.33 (1 H, s, 13-H), 6.15 (2 H, m, 5-H and 11-H),

5.93 (1 H, m, 15-H), 4.74 (2 H, m, OCH₂), 2.30 (3 H, s, NCH₃);

2.21, 1.99 and 1.53 (2:2:4 H, m each, 16-H₂-19-H₂), 1.66 [6 H,

s, 7-(CH₃)₂], 1.15 (OCH₂CH₃). ¹³C NMR (100 MHz, C₆D₆, 300

K): δ 291.3 (C_q, C2), 203.1 and 199.6 [C_qeach, cis- and trans-

CO W(CO)₅], 168.4 (C_q, C6), 156.1 (CH, C4), 154.3 (C_q, C3),

143.6 (C_q, C11a), 143.2 and 138.4 (C_qeach, C12 and C14), 140.3

(C_q, C7a), 139.3 (C_q, i-C Ph), 129.4 (CH, C13), 129.0 (CH, o-C

Ph), 128.4 (CH, m-C Ph), 128.1 (CH, C10), 126.9 (CH, p-C Ph),

122.7 and 122.0 (CH each, C8 and C9), 108.0 (CH, C11), 97.7

(CH, C5), 77.5 (OCH₂), 47.5 (C_q, C7), 28.7 (NCH₃); 28.6, 26.0,

23.5, and 22.6 (CH₂each, C16-C19), 28.1 [CH₃, 7-(CH₃)₂], 15.2

(OCH₂CH₃). IR (diffuse reflection), cm^-1(%): 2926 (4), 2053

(16), 1908 (100), 1559 (34), 1160 (27), 1108 (39). IR (hexane),

cm^-1(%): 2058.1 (7), 1929.1 (100), 1567.8 (15). MS (70 eV),

¹⁸⁴W m/e (%): 705 [M⁺- 2 × CO] (3), 677 [M⁺- 3 × CO] (18),

C3), 131.5 (CH, C11), 129.1 (CH, o-C Ph), 128.7 (CH, p-C Ph),

128.2 (CH, m-C Ph), 128.1 (CH, C9), 124.4 (CH, C10), 124.1

(CH, C7), 123.3 (C_q, C8a), 115.2 (CH, C12), 107.1 (CH, C5),

75.9 (OCH₂), 37.5 (NCH₃), 15.1 (OCH₂CH₃). IR (diffuse reflec-

tion), cm^-1(%): 2050 (34), 1968 (10), 1908 (100). MS (70 eV),

m/e (%): 352 (33), 315 (52), 286 (100), 270 (85), 256 (12), 243

(29), 213 (38), 184 (48). Anal. Calcd for C₂₇H₂₁NO₆W (639.3):

C, 50.73; H, 3.31; N, 2.19. Found: C, 50.87; H, 3.16; N, 2.12.

649 [M⁺- 4 × CO] (10), 621 [M⁺- 5 × CO] (58), 437 [M⁺

-

1

16a . H NMR (400 MHz, C₆D₆, 300 K): δ 7.45 (2 H, m, o-H

W(CO)₅] (44), 422 (75), 408 (88), 301 (14), 283 (20) 171 (100).

Anal. Calcd for C₃₆H₃₅NO₆W (761.5): C, 56.78; H, 4.63; N, 1.84.

Found: C, 56.38; H, 4.65; N, 1.56.

Ph), 7.19 (2 H, m, m-H Ph), 7.13 (1 H, m, p-H Ph), 7.07 (1 H,

m, 7′-H), 6.84 (1 H, m, 5′-H), 6.64 (1 H, m, 6′-H), 6.46 (1 H, m,

3

4

8′-H), 6.44 (1 H, d, J ) 9.6 Hz, 4′-H), 6.18 (1 H, d, J ) 1.7

Hz, 5-H), 5.16 (1 H, d, ⁴J ) 1.7 Hz, 3-H), 5.15 (1 H, d, ³J ) 9.6

Hz, 3′-H), 3.60 (2 H, m, OCH₂CH₃), 2.58 (3 H, s, NCH₃), 1.00

(3 H, t, ³J ) 7.2 Hz, OCH₂CH₃). ¹³C NMR (100 MHz, C₆D₆,

300 K): δ 173.8 (C_q, C2), 145.5 (C_q, C8′a), 141.1 (C_q, C4), 135.6

(C_q, i-C Ph), 129.2 (CH, C7′), 128.8 (CH, m-C Ph), 128.3 (CH,

p-C Ph), 127.9 (CH, C4′), 127.4 (CH, C5′), 126.3 (CH, o-C Ph),

125.2 (CH, C5), 122.7 (CH, C3′), 120.6 (C_q, C4′a), 116.6 (CH,

C6′), 109.6 (CH, C8′), 95.5 (CH, C3), 75.0 (C_q, C1), 66.0 (OCH₂-

CH₃), 32.1 (NCH₃), 14.3 (OCH₂CH₃). IR (diffuse reflection),

cm^-1(%): 2980 (31), 2891 (26), 1618 (64), 1597 (68), 1488 (100),

1350 (80). MS (70 eV), m/e (%): 315 (41) [M⁺], 286 (100), 270

(24), 256 (12), 243 (31), 167 (15). Anal. Calcd for C₂₂H₂₁NO

(315.4): C, 83.78; H, 6.71; N, 4.44. Found: C, 83.65; H, 6.64;

N, 4.26.

Sp ir o[2-et h oxy-4-p h en ylcyclop en t a -2,4-d ien e-1,2′-N-

eth yl-1′,2′-d ih yd r oqu in olin e] (16b). 1,2-Dimethylquinolin-

ium tetrafluoroborate (10b) (259 mg, 1.0 mmol) and penta-

carbonyl(1-ethoxy-3-phenylpropyn-1-ylidene)tungsten (1a )

(482 mg, 1.0 mmol) were reacted in a 100 mL flask with

triethylamine (152 mg 1.5 mmol) in 15 mL of dichloremethane

as described above to give compound 16b as a colorless oil (231

mg, 70%, R_f) 0.8 on silica gel with n-pentane/diethyl ether,

10:1). A single crystal suitable for X-ray diffraction was

obtained from the NMR sample of compound 16b in C₆D₆at

20 °C.

P en t a ca r bon yl[1-et h oxy-3-p h en yl-4-(1-m et h ylch in a l-

d in -2-ylid en e)bu t-2-en ylid en e]tu n gten (14a ) a n d Sp ir o-

[2-et h oxy-4-p h en ylcyclop en t a -2,4-d ien e-1,2′-N-m et h yl-

1′,2′-d ih yr oqu in olin e] (16a ). To 1,2-dimethylquinolinium

iodide (10a ) (285 mg, 1.0 mmol) and pentacarbonyl(1-ethoxy-

3-phenylpropyn-1-ylidene)tungsten (1a ) (482 mg, 1.0 mmol)

in a 4 mL screw-top vessel was added 0.5 mL of a 4 M aqueous

NaOH solution and then 3 mL of diethyl ether. The mixture

was vigorously shaken for 1 min, cleared by centrifugation,

and stored for 20 h at -40 °C. The sample was then allowed

to warm to the melting point of the aqueous phase while

centrifugation was continued to afford a dark blue etheral

phase (which was discarded) and dark blue crystalline com-

pound 14a in the aqueous phase. The compound was analyti-

cally clean after drying in vacuo (10^-3mbar) for 2 h. It was

shown by NMR spectra that compound 14a was quantitatively

transformed into compound 16a at 30 °C within 6 h. A sample

of compound 16a was also obtained by reaction of 1,2-

dimethylquinolinium iodide (10a ) (285 mg, 1.0 mmol) with

pentacarbonyl(1-ethoxy-3-phenylpropyn-1-ylidene)tungsten (1a)

(482 mg, 1.0 mmol) in a 100 mL flask with 152 mg (1.5 mmol)

of triethylamine in 15 mL of dichloromethane. After stirring

for 10-20 min at 20 °C a color change from brown to blue was

observed and compound 1a was completely consumed (TLC

test). The solvent was removed in vacuo, and the residue was

extracted with 2 × 40 mL each of diethyl ether and filtered

through Celite. After 12 h at 20 °C the color of the solution

had changed from blue to brown and compound 16a was

isolated by chromatography on alumina and removal of the

eluant as a colorless oil (227 mg, 72%, R_f) 0.8 on silica gel

with n-pentane/diethyl ether, 10:1).

1

16b. H NMR (400 MHz, C₆D₆, 300 K): δ 7.46 (2 H, m, o-H

Ph), 7.21 (2 H, m, m-H Ph), 7.13 (1 H, m, p-H Ph); 7.07 (1 H,

m, 7′-H), 6.85 (1 H, m, 5′-H), 6.63 (1 H, m, 6′-H), 6.50 (1 H, m,

3

14a . ¹H NMR (600 MHz, CD₂Cl₂, 213 K): δ 7.76 (1 H, m,

11-H), 7.68 (1 H, m, 12-H), 7.58 (1 H, m, 9-H), 7.50 (3 H, m, o-

and p-H Ph), 7.43 (3 H, m, m-H Ph and 10-H), 7.36 (1 H, s,

5-H), 7.26 (1 H, d, ³J ) 9.6 Hz, 8-H), 6.64 (1 H, s, 3-H), 6.43 (1

d, J ) 8.3 Hz, 8′-H), 6.43 (1 H, d J ) 10.0 Hz, 4′-H), 6.22 (1

H, d, ⁴J ) 1.8 Hz, 5-H), 5.15 (1 H, d, ⁴J ) 1.8 Hz, 3-H), 5.09 (1

H, d, ³J ) 10.0 Hz, 3′-H), 3.57 (2 H, q, ³J ) 7.0 Hz, OCH₂-

CH₃), 3.03 (2 H, m, NCH₂CH₃), 1.10 (3 H, t, ³J ) 7.0 Hz,

NCH₂CH₃), 0.99 (3 H, t, ³J ) 7.0 Hz, OCH₂CH₃). ¹³C NMR

(100 MHz, C₆D₆, 300 K): δ 174.6 (C_q, C2), 144.1 (C_q, C8′a),

140.6 (C_q, C4), 135.8 (C_q, i-C Ph), 129.4 (CH, C7′), 128.9 (CH,

m-C Ph), 128.3 (CH, p-C Ph), 128.0 (CH, C4′ and C5′), 126.4

(CH, o-C Ph), 125.9 (CH, C5), 122.5 (CH, C3′), 120.5 (C_q, C4′a),

3

H, d, J ) 9.6 Hz, 7-H), 4.59 (2 H, m, dyn. br OCH₂), 4.00 (3

h, s, NCH₃), 1.61 (3 H, m, dyn. br OCH₂CH₃). ¹³C NMR (150

MHz, CD₂Cl₂, 213 K): δ 259.5 (C_q, C2), 204.9 and 199.4 [C_q

each, trans- and cis-CO W(CO)₅], 157.3 (C_q, C6), 149.3 (C_q, C3),

142.1 (C_q, i-C Ph), 139.1 (C_q, C12a), 132.9 (CH, C8), 132.2 (CH,

Spiro-Fused Cyclopentadienes

Organometallics, Vol. 20, No. 13, 2001 2903

116.3 (CH, C6′), 109.7 (CH, C8′), 95.7 (CH, C3), 75.2 (C_q, C1),

66.0 (OCH₂CH₃), 40.4 (NCH₂CH₃), 14.4 (OCH₂CH₃), 13.9

(NCH₂CH₃). IR (diffuse reflection), cm^-1(%): 29 77 (26), 1615

(24), 1597 (31), 1487 (54), 1342 (48), 1112 (30), 743 (100). MS

(70 eV), m/e (%): 329 (90) [M⁺], 300 (100), 284 (32), 272 (37),

256 (14), 243 (59), 167 (8), 128 (13). Anal. Calcd for C₂₃H₂₃NO

(329.4): C, 83.85; H, 7.04; N, 4.25. Found: C, 83.70; H, 7.21;

N, 4.03. X-ray crystal structure analysis of 16b:²²formula

described above to give colorless compound 17d (240 mg, 73%,

R_f) 0.7 on silica gel with n-pentane/diethyl ether, 10:1). A

single crystal suitable for X-ray diffraction was obtained from

the NMR sample of compound 17d in C₆D₆at 20 °C.

17d . H NMR (400 MHz, C₆D₆, 300 K): δ 7.56 (2 H, m, o-H

Ph), 7.20 (2 H, m, m-H Ph), 7.17 (1 H, m, 5′-H), 7.12 (1 H, m,

1

p-H Ph), 7.03 (1 H, m, 7′-H), 6.77 (1 H, m, 6′-H), 6.54 (2 H, m,

3

8′-H and 5-H), 5.99 (1 H, d, J ) 8.0 Hz, 2′-H), 5.32 (1 H, d,

⁴J ) 1.5 Hz, 3-H), 4.44 (1 H, d, ³J ) 8.0 Hz, 3′-H), 3.63

(2 H, m, OCH₂CH₃), 3.01 (2 H, m, NCH₂CH₃), 0.98 (3 H, t,

³J ) 7.0 Hz, OCH₂CH₃), 0.94 (3 H, ³J ) 7.2 Hz, NCH₂CH₃).

¹³C NMR (100 MHz, C₆D₆, 300 K): δ 179.1 (C_q, C2), 140.0 and

139.8 (C_qeach, C8′a and C4), 136.5 (C_q, i-C Ph), 132.5 and

132.4 (CH each, C2′ and C5), 128.8 and 128.5 (CH each, m-

and p-C Ph), 127.6 (CH, C5′), 126.3 (CH, o-C Ph), 121.4

(C_q, C4′a), 120.7 (CH, C6′), 112.4 (CH, C8′), 97.6 (CH, C3′),

95.1 (CH, C3), 65.8 (OCH₂CH₃), 56.7 (C_q, C1), 44.8 (NCH₂CH₃),

14.3 (OCH₂CH₃), 12.8 (NCH₂CH₃). IR (diffuse reflection), cm^-1

(%): 2975 (24), 1659 (18), 1599 (25), 1484 (41), 1387 (46),

1110 (30), 748 (100). MS (70 eV), m/e (%): 329 (65) [M⁺], 300

(100), 284 (17), 272 (40), 254 (13), 242 (41), 215 (12). Anal.

Calcd for C₂₃H₂₃NO (329.4): C, 83.85; H, 7.04; N, 4.25.

Found: C, 83.54; H, 6.81; N, 4.08. X-ray crystal structure

analysis of 17d :²²formula C₂₃H₂₃NO, M ) 329.42, light yellow

crystal 0.45 × 0.35 × 0.10 mm, a ) 10.812(1) Å, b ) 8.533(1)

Å, c ) 19.789(2) Å, â ) 96.85(1)°, V ) 1812.7(3) Å³, F_calc) 1.207

g cm^-3, µ ) 5.65 cm^-1, empirical absorption correction via ψ

scan data (0.785 e T e 0.946), Z ) 4, monoclinic, space group

P2₁(No. 4), λ ) 1.54178 Å, T ) 223 K, ω/2θ scans, 4165

reflections collected (-h, -k, (l), [(sin θ)/λ] ) 0.62 Å^-1, 3952

independent (R_int) 0.030) and 3358 observed reflections [I g

2σ(I)], 456 refined parameters, R ) 0.048, wR₂) 0.135, max.

residual electron density 0.22 (-0.20) e Å^-3, Flack parameter

0.0(5), two independent molecules in the asymmetric unit,

nearly enantiomorphic, difference in the position of the phenyl

group C20 to C25, hydrogens calculated and refined as riding

atoms.

C

₂₃H₂₃NO‚0.5 C₆H₆, M ) 368.48, yellow crystal 0.45 × 0.30 ×

0.20 mm, a ) 11.100(1) Å, b ) 16.841(1) Å, c ) 11.111(1) Å, â

) 95.05(1)°, V ) 2069.0(3) Å³, F_calc) 1.183 g cm^-3, µ ) 0.71

cm^-1, absorption correction via SORTAV (0.969 e T e 0.986),

Z ) 4, monoclinic, space group P2₁/n (No. 14), λ ) 0.71073 Å,

T ) 293 K, ω and æ scans, 12 070 reflections collected ((h,

(k, (l), [(sin θ)/λ] ) 0.71 Å^-1, 5834 independent (R_int) 0.035)

and 3997 observed reflections [I g 2σ(I)], 255 refined param-

eters, R ) 0.057, wR₂) 0.136, max. residual electron density

0.22 (-0.23) e Å^-3, hydrogens calculated and refined as riding

atoms.

Sp ir o[2-et h oxy-4-p h en ylcyclop en t a -2,4-d ien e-1,4′-N-

m eth yl-1′,4′-d ih yd r oqu in olin e] (17c). 1,4-Dimethylquino-

linium iodide (11c) (285 mg, 1.0 mmol) and pentacarbonyl(1-

ethoxy-3-phenylpropyn-1-ylidene)tungsten (1a ) (482 mg, 1.0

mmol) in a 100 mL flask were reacted with triethylamine (152

mg, 1.5 mmol) in 15 mL of dichloromethane as described above

to give colorless compound 17c (234 mg, 74%, R_f) 0.6 on silica

gel with n-pentane/diethyl ether, 10:1).

1

17c. H NMR (400 MHz, C₆D₆, 300 K): δ 7.57 (2 H, m, o-H

Spir o[2-eth oxy-5-m eth yl-4-ph en ylcyclopen ta-2,4-dien e-

1,4′-N-m eth yl-1′,4′-d ih yd r op yr id in e] (17e). 4-Ethyl-1-meth-

ylpyridinium iodide (11e) (249 mg, 1.0 mmol) and pentacar-

bonyl(1-ethoxy-3-phenylpropyn-1-ylidene)tungsten (1a ) (482

mg, 1.0 mmol) in a 100 mL flask were reacted with triethyl-

amine (152 mg, 1.5 mmol) in 15 mL of dichloromethane as

described above to give colorless compound 17e (191 mg, 68%,

R_f) 0.5 on silica gel with n-pentane/diethyl ether, 10:1), which

turned cherry-red after contact with air.

Ph), 7.20 (2 H, m, m-H Ph), 7.16 (1 H, m, 5′-H), 7.12 (1 H, m,

p-H Ph), 7.05 (1 H, m, 7′-H), 6.79 (1 H, m, 6′-H), 6.55 (1 H, d,

3

⁴J ) 1.9 Hz, 5-H), 6.45 (1 H, d, J ) 7.7 Hz, 8′-H), 5.92 (1 H,

d, ³J ) 8.0 Hz, 2′-H), 5.33 (1 H, d, ⁴J ) 1.9 Hz, 3-H), 4.48 (1 H,

3

d, J ) 8.0 Hz, 3′-H), 3.63, (2 H, m, OCH₂CH₃), 2.47 (3 H, s,

NCH₃), 0.97 (3 H, t, ³J ) 7.0 Hz, OCH₂CH₃). ¹³C NMR (100

MHz, C₆D₆, 300 K): δ 179.1 (C_q, C2), 141.0 (C_q, C8′a), 139.9

(C_q, C4), 136.5 (C_q, i-C Ph), 133.8 (CH, C2′), 132.7 (CH, C5),

128.7 (CH, o-C Ph), 128.1 and 127.9 (CH each, p-C Ph and

C5′), 127.6 (CH, C7′), 126.3 (CH, o-C Ph), 121.0 (C_q, C4′a),

120.9 (CH, C6′), 112.3 (CH, C8′), 97.0 (CH, C3′), 95.1 (CH, C3),

65.8 (OCH₂CH₃), 56.6 (C_q, C1), 37.8 (NCH₃), 14.3 (OCH₂CH₃).

IR (diffuse reflection), cm^-1(%): 2978 (31), 2908 (32),

1660 (13), 1600 (19), 1481 (39), 1359 (39), 1103 (42), 748 (100).

MS (70 eV), m/e (%): 315 (60) [M⁺], 286 (100), 270 (21), 257

(19), 242 (27), 166 (13), 155 (23). Anal. Calcd for C₂₂H₂₁NO

(315.4): C, 83.78; H, 6.71; N, 4.44. Found: C, 83.98; H, 6.96;

N, 4.10.

1

Sp ir o[2-et h oxy-4-p h en ylcyclop en t a -2,4-d ien e-1,4′-N-

eth yl-1′,4′-d ih yd r oqu in olin e] (17d ). 1,4-Dimethylquinolin-

ium tetrafluoroborate (11d ) (259 mg, 1.0 mmol) and penta-

carbonyl(1-ethoxy-3-phenylpropyn-1-ylidene)tungsten (1a) (482

mg, 1.0 mmol) in a 100 mL flask were reacted with triethyl-

amine (152 mg,1.5 mmol) in 15 mL of dichloromethane as

17e. H NMR (400 MHz, C₆D₆, 300 K): δ 7.56 (2 H, m, o-H

Ph), 7.28 (2 H, m, m-H Ph), 7.17 (1 H, p-H Ph), 5.85 (2 H, m,

2′-H and 6′-H), 5.18 (1 H, s, 3-H), 4.24 (2 H, m, 3′-H and 5′-H),

3.71 (2 H, q, ³J ) 7.1 Hz, OCH₂CH₃), 2.29 (3 H, s, NCH₃), 2.20

(3 H, s, 5-CH₃), 1.16 (3 H, t, ³J ) 7.1 Hz, OCH₂CH₃). ¹³C NMR

(100 MHz, C₆D₆, 300 K): δ 176.1 (C_q, C2); 138.6, 138.5, and

133.9 (C_qeach, C4, C5 and i-C Ph), 133.0 (CH, C2′ and C6′);

128.5, 128.4, and 126.6 (CH each, o-, m-, and p-C Ph), 99.8

(CH, C3′ and C5′), 98.0 (CH, C3), 65.3 (OCH₂CH₃), 56.7 (C_q,

C1), 40.0 (NCH₃), 14.6 (OCH₂CH₃), 12.5 (CH₃, 5-CH₃). IR

(diffuse reflection), cm^-1(%): 2978 (25), 2906 (29), 1673 (42),

1580 (61), 1374 (56), 1203 (100). MS (70 eV), m/e (%): 279 (100)

[M⁺], 250 (66), 234 (88), 220 (16), 207 (22), 192 (11), 178 (7).

Anal. Calcd for C₁₉H₂₁NO (279.4): C, 81.68; H, 7.58; N, 5.01.

Found: C, 81.37; H, 7.82; N, 4.91.

2904 Organometallics, Vol. 20, No. 13, 2001

Go¨ttker-Schnetmann et al.

N-Meth ylp yr id in iu m -4-[(1E/Z,3E)-(2-eth oxy-4-p h en yl-

1,3-bu ta d ien -3-yl]p en ta ca r bon yltu n gsta te (18f/18′f). 1,4-

Dimethylpyridinium iodide (11f) (235 mg, 1.0 mmol) and

pentacarbonyl(1-ethoxy-3-phenylpropyn-1-ylidene)tungsten (1a)

(482 mg, 1.0 mmol) in a 4 mL screw-top vessel were reacted

with triethylamine (152 mg, 1.5 mmol) in 3.5 mL of dichloro-

methane. Compound 1a was consumed at 20 °C, 5 min while

stirring (TLC test). Flash chromatography on silica gel with

diethyl ether/methanol, 20:1, afforded compounds 18f/18′f as

an orange oil (312 mg, 0.53 mmol, 53%, R_f) 0.5 in diethyl

ether/methanol, 20:1). An orange powder insoluble in C₆D₆,

but soluble in CD₂Cl₂or CDCl₃, was obtained from the NMR

orange crystal 0.40 × 0.30 × 0.10 mm, a ) 9.880(1) Å, b )

14.654(1) Å, c ) 17.779(1) Å, â ) 95.20(1)°, V ) 2563.5(3) Å³,

F

SORTAV (0.252 e T e 0.648), Z ) 4, monoclinic, space group

P2₁/n (No. 14), λ ) 0.71073 Å, T ) 198 K, ω and æ scans, 17 426

reflections collected ((h, (k, (l), [(sin θ)/λ] ) 0.62 Å^-1, 5047

independent (R_int) 0.049) and 4122 observed reflections [I g

2σ(I)], 309 refined parameters, R ) 0.031, wR₂) 0.066, max.

residual electron density 1.41 (-0.92) e Å^-3, hydrogens calcu-

lated and refined as riding atoms.

_calc) 1.747 g cm^-3, µ ) 47.53 cm^-1, absorption correction via

N-E t h ylp yr id in iu m -4-[(1E/Z,3E)-(2-et h oxy-4-p h en yl-

1,3-b u t a d ien -3-yl)]p en t a ca r b on ylt u n gst a t e (18g/18′g).

1-Ethyl-4-methylpyridinium tetrafluoroborate (11g) (209 mg,

1.0 mmol) and pentacarbonyl(1-ethoxy-3-phenylpropyn-1-

ylidene)tungsten (1a ) (482 mg, 1.0 mmol) in a 4 mL screw-top

vessel were reacted with triethylamine (152 mg, 1.5 mmol) in

3.5 mL of dichloromethane as described above to give com-

pounds 18g/18′g as an orange oil after flash chromatography

on silica gel with diethyl ether/methanol, 20:1 (306 mg, 0.51

mmol, 51%, R_f) 0.5 in diethyl ether/methanol, 20:1).

1

sample in C₆D₆after removal of the solvent. However H NMR

spectra of this powder in CD₂Cl₂were found to be identical

with that of the orange oil obtained iniatially. Compounds 18f/

18′f were stable in (C₆D₆, CDCl₃, or CD₂Cl₂) solution at 300 K

for several hours. Single crystals of the major isomer 18f

suitable for an X-ray diffraction analysis were obtained from

CH₂Cl₂after 48 h at 233 K.

1

18f. H NMR (600 MHz, CD₂Cl₂, 213 K; mixture of isomers

18f and 18′f, minor isomer 18′f in brackets): δ 7.99 {8.12} (1

H, “d”, br, 4-H), 7.42 {7.49} (1 H, “d”, br, 1-H), 7.33 {7.32} (1

H, “d”, br, 5-H), 7.21 {7.21} (4 H, m, o-H and m-H Ph), 7.12

{6.96} (1 H, “t”, 1:12:1, ³J (¹H,¹⁸³W) ) 6.8 Hz, 9-H), 7.07 {7.14}

(1 H, m, p-H Ph), 6.91 {6.72} (1 H, “d”, br, 2-H), 5.38 {5.16} (1

H, s, 6-H), 4.35 and 3.82 {4.52 and 3.93} (1:1 H, m each, OCH₂),

3.96 {3.76} (3 H, s, NCH₃), 1.33 {1.47} (3 H, t, ³J ) 7.1 Hz,

OCH₂CH₃). ¹³C NMR (150 MHz, CD₂Cl₂, 213 K; mixture of

isomers, minor isomer in brackets): δ 204.2 and 200.7 {205.7

and 200.9} [C_qeach, trans- and cis-CO W(CO)₅], 188.3 {189.2}

(C_q, C8), 163.2 {163.1} (C_q, C7), 152.1 {152.0} (C_q, C3), 139.6

{138.8} (C_q, i-C Ph), 139.5 {139.8} (CH, C1), 138.5 {138.7} (CH,

C5), 137.2 {135.6} (CH, C9), 128.3 {128.3} (CH, m-C Ph), 126.2

{125.2} (CH, p-C Ph), 125.9 {125.5} (CH, o-C Ph), 120.8

{120.6} (CH, C2), 118.0 {117.5} (CH, C4), 90.1 {92.0} (CH,

C6), 63.0 {64.7} (OCH₂), 44.9 {44.7} (NCH₃), 14.2 {14.7}

(OCH₂CH₃). ¹H NMR (400 MHz, C₆D₆, 300 K; mixture of

isomers, minor isomer in brackets): (2- and 4-H not detected

due to dynamical line broadening) δ 7.59 {7.50} (1 H, “t”, 1:12:

1, ³J (¹H,¹⁸³W) ) 6.8 Hz, 9-H), 7.33 {7.31} (2 H, m, o-H Ph),

7.10 {7.13} (2 H, m, o-H Ph), 6.92 {6.94} (1 H, m, p-H Ph),

18g. ¹H NMR (360 MHz, C₆D₆, 303 K; mixture of isomers

18g and 18′g, minor isomer 18′g in brackets): (2- and 4-H

were not detected due to dynamical line broadening) δ 7.63

3

{7.52} (1 H, “t”, J (¹H,¹⁸³W) ) 6.6 Hz, 9-H), 7.37 {7.32} (2 H,

m, o-H Ph), 7.09 {7.12} (2 H, m, m-H Ph), 6.92 {6.94} (1 H, m,

p-H Ph), 5.94 {5.98} (2 H, ³J ) 7.1 Hz, 1- and 5-H), 5.47 {5.37}

(1 H, s, 6-H), 4.53 and 3.93 {4.72 and 4.06} (1:1 H, m, each,

3

OCH₂), 2.44 {2.64} (2 H, NCH₂), 1.15 {1.26} (3 H, t, J ) 7.1

Hz, OCH₂CH₃), 0.34 {0.52} (3 H, t, ³J ) 7.4 Hz, NCH₂CH₃).

¹³C NMR (90 MHz, C₆D₆, 303 K; mixture of isomers, minor

isomer in brackets): δ 203.9 and 202.0 {205.6 and 202.3} [C_q

each, trans- and cis-CO W(CO)₅], 190.5 {190,2} (C_q, C8), 164.8

{164.3} (C_q, C7), 152.6 {152.4} (C_q, C3), 141.2 {140.5} C_q, i-C

Ph), 138.5 and 136.9 {138.5 and 136.9} CH each, C1, C5 and

C9), 129.1 {129.0} (CH, o-C Ph), 126.8 {127.5} (CH, m-C Ph),

126.5 {126.0} (CH, p-C Ph), 119.7 {119.7} (C2 and C4),

93.1 {94.7} (CH, C6), 63.8 {65.7} (OCH₂), 52.3 {52.3} (NCH₂),

15.3 {15.6} (NCH₂CH₃), 14.9 {15.2} (OCH₂CH₃). IR (CH₂Cl₂),

cm^-1(%): 2051 (13), 1959 (7), 1910 (100), 1871 (25). MS

(MALDI-TOF, matrix: DCTB): 603 [M⁺], 575 [M⁺- CO], 547

[M⁺- 2 × CO].

3

5.77 {5.85} (2 H, d, J ) 8.0 Hz, 1-and 5-H), 5.42 {5.33} (1 H,

s, 6-H), 4.50 and 3.93 {4.68 and 4.04} (1:1 H, m each, OCH₂),

2.04 {2.29} (3 H, s, NCH₃), 1.15 {1.24} (3 H, t, ³J ) 7.1 Hz,

OCH₂CH₃). ¹³C NMR (100 MHz, C₆D₆, 300 K; mixture of

isomers, minor isomer in brackets): δ 204.0 and 202.0 {205.5

and 202.2} (C_qeach, trans- and cis-CO W(CO)₅), 190.5 {190.3}

(C_q, C8), 164.6 {164.3} (C_q, C7), 152.3 {152.1} (C_q, C3), 141.2

{140.5} (C_q, i-C Ph), 138.4 {138.2} (CH, C1 and C5), 137.0

{137.0} (CH, C9), 128.9 {128.8} (CH, m-C Ph), 126.7 {127.4}

(CH, o-C Ph), 126.3 {125.9} (CH, p-C Ph), 119.4 {119.4} (C2

and C4, but no cross-peak in the GHSQC and no signal in the

DEPT 135 experiment), 93.0 {94.8} (CH, C6), 63.7 {65.6}

(OCH₂), 43.1 {43.1} (NCH₃), 14.7 {15.0} (OCH₂CH₃). IR (CH₂-

Cl₂), cm^-1(%): 2051 (15), 1959 (8), 1911 (100), 1870 (26). MS

(MALDI-TOF, 337.0 nm, 3 ns, matrix: DCTB²⁴): 589 [M⁺],

561 [M⁺- CO], 533 [M⁺- 2 × CO]. X-ray crystal structure

analysis of 18f:²²formula C₂₃H₁₉NO₆W‚CH₂Cl₂, M ) 674.17,

Ack n ow led gm en t . This investigation was sup-

ported by the Deutsche Forschungsgemeinschaft (grant

of the Graduiertenkolleg “Hochreaktive Mehrfachbin-

dungssysteme” at Mu¨nster to I.G.-S.) and the Fonds der

Chemischen Industrie.

Su p p or tin g In for m a tion Ava ila ble: Details of the X-ray

crystal structure analyses. This material is available free of

charge via the Internet at http://pubs.acs.org.

(24) DCTB ) 1,1-dicyano-3-methyl-4-(4-tert-butylphenyl)-1,3-butene.

OM010117B

Article Doi

Spiro-fused cyclopentadienes and novel pyridinium carbonyltungstates from (1-alkynyl)carbene tungsten complexes and exo-methylene n-heterocycles. Competition between 1,4-addition, 1,2-addition, and metathesis

DOI: 10.1021/om010117b

Source and publish data:

Authors:

Article abstract of DOI:10.1021/om010117b

Full text of DOI:10.1021/om010117b

Products guided by the article

R&D Labs maybe for 352560-08-8

Relevant to this article

Hot Product