Organic syntheses via transition metal complexes. 85. [2-(Alkenyloxy)ethenyl]- and [2-(aryloxy)ethenyl]carbene complexes from (1-alkynyl)carbene complexes of chromium and tungsten and their fragmentation to 2,4-dien-5-ones

Article abstract of DOI:10.1021/om9604132

[2-(Alkenyloxy)ethenyl]carbene complexes (CO)⁵M=C(OEt)CH=C(O-alkenyl)Ph (3) (M = Cr, W) are obtained by base-catalyzed O-addition of enolizable 1,3-diones 2 (cyclopentane-1,3-dione and dimedone) to (1-alkynyl)carbene complexes (CO)₅M=C(OEt)C≡CPh (1) (M = Cr, W) together with pyran-2-ylidene complexes 4, which are generated by C-addition of the enolate unit of 2. Thermal fragmentation of the O-addition products 3 affords dienones 5, resulting from overall C₃ insertion of the (l-alkynyl)carbene ligand of 1 into a C,O bond of 2. Both, O- and C-addition products, 7 and 8, respectively, are derived from reaction of 9-phenanthrol (6) with 1 in a ratio 2:1, but phenol (9a) and 2-naphthol (9b) yield [2-(aryloxy)-ethenyl]carbene complexes (CO)₅M=C(OEt)CH=C(OAr)Ph (10) (M = Cr, W; Ar = Ph, 2-naphthyl) only (81-91%). Addition of 9 is highly regio- and stereoselective and affords stereoisomers (E)-10 initially, which undergo (E/Z) isomerization in solution to give isomers (Z)-10. Binuclear carbene complexes 12, 14, and 16 [(CO)₅M=C(OEt)CH=C(Ph)OArO-(Ph)C=CH(OEt)C=M(CO)₅ (M = Cr, W)] are obtained from dihydroxyaryl compounds Ar(OH)₂ (Ar = 1,4-phenylene, 1,3-phenylene, 1,1?-binaphthyl). Addition of cyclohexyl isocyanide (17) to (Z)-10 results in formation of a ketenmine complex (CO)₅Cr[CyN=C=C-(OEt)CH=C(OPh)Ph], which in the presence of water and (excess) 17 affords an (1-amino)-ketocarbene complex (CO)₅Cr=C(NHCy)C(=O)CH=C(OPh)Ph (18) and an amide (CyNH)C-(=O)CH(OEt)CH=C(OPh)Ph (19). X-ray data are reported for compounds (Z)-3b, (E)-10d, and (E,E)- 12a.

Full text of DOI:10.1021/om9604132

4842
Organometallics 1996, 15, 4842-4851
Or ga n ic Syn th eses via Tr a n sition Meta l Com p lexes. 85.1
[2-(Alk en yloxy)eth en yl]- a n d [2-(Ar yloxy)eth en yl]ca r ben e
Com p lexes fr om (1-Alk yn yl)ca r ben e Com p lexes of
Ch r om iu m a n d Tu n gsten a n d Th eir F r a gm en ta tion to
2,4-Dien -5-on es
Rudolf Aumann,* Roland Fro¨hlich, and Sirpa Kotila
Organisch-Chemisches Institut der Universita¨t Mu¨nster, Corrensstrasse 40,
D-48149 Mu¨nster, Germany
Received May 28, 1996X
[2-(Alkenyloxy)ethenyl]carbene complexes (CO)5MdC(OEt)CHdC(O-alkenyl)Ph (3) (M )
Cr, W) are obtained by base-catalyzed O-addition of enolizable 1,3-diones 2 (cyclopentane-
1,3-dione and dimedone) to (1-alkynyl)carbene complexes (CO)5MdC(OEt)CtCPh (1) (M )
Cr, W) together with pyran-2-ylidene complexes 4, which are generated by C-addition of
the enolate unit of 2. Thermal fragmentation of the O-addition products 3 affords dienones
5, resulting from overall C3 insertion of the (1-alkynyl)carbene ligand of 1 into a C,O bond
of 2. Both, O- and C-addition products, 7 and 8, respectively, are derived from reaction of
9-phenanthrol (6) with 1 in a ratio 2:1, but phenol (9a ) and 2-naphthol (9b) yield [2-(aryloxy)-
ethenyl]carbene complexes (CO)5MdC(OEt)CHdC(OAr)Ph (10) (M ) Cr, W; Ar ) Ph,
2-naphthyl) only (81-91%). Addition of 9 is highly regio- and stereoselective and affords
stereoisomers (E)-10 initially, which undergo (E/Z) isomerization in solution to give isomers
(Z)-10. Binuclear carbene complexes 12, 14, and 16 [(CO)5MdC(OEt)CHdC(Ph)OArO-
(Ph)CdCH(OEt)CdM(CO)5 (M ) Cr, W)] are obtained from dihydroxyaryl compounds
Ar(OH)2 (Ar ) 1,4-phenylene, 1,3-phenylene, 1,1′-binaphthyl). Addition of cyclohexyl
isocyanide (17) to (Z)-10 results in formation of a ketenmine complex (CO)5Cr[CyNdCdC-
(OEt)CHdC(OPh)Ph], which in the presence of water and (excess) 17 affords an (1-amino)-
ketocarbene complex (CO)5CrdC(NHCy)C(dO)CHdC(OPh)Ph (18) and an amide (CyNH)C-
(dO)CH(OEt)CHdC(OPh)Ph (19). X-ray data are reported for compounds (Z)-3b, (E)-10d ,
and (E,E)-12a .
1-Meta lla -2,4-d ioxy-1,3-bu ta d ien es. 1-Metalla-1,3-
bonyl equivalents and the synthethic implications based
on such a relationship. 1-Metalla-1,3-butadienes have
been prepared as early as 1967,5 but systematic studies
were initiated only recently. Several methods are
available for the generation of complexes (CO)5MdC-
(OEt)CdCR(O-alkyl) (M ) Cr, W) containing an enol
ether unit. They include (a) condensation of methylcar-
bene complexes (CO)5MdC(OEt)CH3 with nonenolizable
acid amides R1-CONR2,6 (b) reaction of enolizable acid
amides R1CH2-CONR2 with carbene complexes (CO)5Md
C(OEt)R involving insertion of the CCN backbone into
the MdC bond,7 (c) insertion of an alkyne group into
the MdC bond of an alkoxycarbene complex,6b,8,9 and
(d) addition of alcohols to an (1-alkynyl)carbene
complex.10-12 The latter method has been utilized, e.g.,
butadienes2 ()alkenylcarbene complexes) of chromium
and tungsten have gained much interest as C3 building
blocks for the synthesis of carbocyclic and heterocyclic
ring compounds.3,4 Among the broad array of 1-metalla-
1,3-dienes the 2,4-dioxy derivatives (CO)5MdC(OEt)-
CHdCR(OR1) (M ) Cr, W) deserve special attention
with regard to the structural relationship to 1,3-dicar
X Abstract published in Advance ACS Abstracts, October 1, 1996.
(1) Part 84 of this series: Aumann, R.; J asper, B.; Fro¨hlich, R.
Organometallics 1996, 15, 1942.
(2) The term 1-metalla-1,3-butadiene and also 1-metalla-1,3,5-
hexatriene has been suggested (see: Aumann, R.; Heinen, H. Chem.
Ber. 1987, 120, 537-540) to allow for a simple systematic nomenclature
of alkenylcarbene complexes with different substitution pattern and
different stereochemistry.
(3) (a) Do¨tz, K. H. Angew. Chem. 1995, 87, 672-673; Angew. Chem.,
Int. Ed. Engl. 1995, 14, 644. (b) Do¨tz, K. H. Angew. Chem. 1984, 96,
573; Angew. Chem., Int. Ed. Engl. 1984, 23, 587. (c) Do¨tz, K. H. In
Organometallics in Organic Synthesis: Aspects of a Modern Interdis-
ciplinary Field; Tom Dieck, H., de Meijere, A., Eds.; Springer Verlag:
Berlin, 1988. (d) Wulff, W. D. In Comprehensive Organic Synthesis;
Trost, B. M., Fleming, I., Eds.; Pergamon Press: Oxford, U.K., 1991;
Vol. 5, pp 1065-1113. (e) Wulff, W. D. In Comprehensive Organome-
tallic Chemistry II; Abel, A. W., Stone, F. G. A., Wikinson, G., Eds.;
Pergamon Press: Oxford, U.K., 1995; Vol. 12, p 469 ff. (f) Hegedus, L.
S. In Comprehensive Organometallic Chemistry II; Abel, A. W., Stone,
F. G. A., Wikinson, G., Eds.; Pergamon Press: Oxford, U.K., 1995; Vol.
12, p 549 ff. (g) Duetsch, M.; Lackmann, R.; Stein, F.; deMeijere, A.
Synlett 1991, 324-326. Flynn, B.; Silveira, C.; deMeijere, A. Synlett
1995, 812-814. (h) Barluenga, J .; Aznar, F.; Valde´s, C.; Mart´ın, A.;
Garc´ıa-Granda, S.; Mart´ın, E. J . Am. Chem. Soc. 1993, 115, 4403-
4404. (i) Barluenga, J .; Aznar, F.; Mart´ın, A.; Vazquez, J . T. J . Am.
Chem. Soc. 1995, 117, 9419-9426. (j) Merlic, A.; Xu, D. J . Am. Chem.
Soc. 1991, 113, 7418-7419.
(4) (a) Hegedus, L. S. Pure Appl. Chem. 1990, 62, 691-698. (b)
Review: Aumann, R. Angew. Chem. 1988, 100, 1512-1524; Angew.
Chem., Int. Ed. Engl. 1988, 27, 1456-1467. (c) Aumann, R.; Hinter-
ding, P.; Kru¨ger, C.; Betz, P. Chem. Ber. 1990, 123, 1847-1852. (d)
Funke, F.; Duetsch, M.; Stein, F.; Noltemeyer, M.; deMeijere, A. Chem.
Ber. 1994, 127, 911-920.
(5) (a) Aumann, R.; Fischer, E. O. Angew. Chem. 1967, 79, 900-
901; Angew. Chem., Int. Ed. Engl. 1967, 6, 879-880. (b) Aumann, R.;
Fischer, E. O. Chem. Ber. 1968, 101, 954-962.
(6) (a) Aumann, R.; Hinterding, P. Chem. Ber. 1990, 123, 611-620.
(b) Aumann, R.; Hinterding, P. Chem. Ber. 1991, 124, 213-218. (c)
Licandro, E.; Maiorana, S.; Papagni, A.; Zanotti Gerosa, A.; Cariati,
F.; Bruni, S.; Chiesi Villa, A. Inorg. Chim. Acta 1994, 220, 233-247.
(7) Aumann. R.; Hinterding, P. Chem. Ber. 1989, 122, 365-370.
(8) Do¨tz, K.-H. Angew. Chem. 1984, 96, 573-594 (see p 576); Angew.
Chem., Int. Ed. Engl. 1984, 23, 587-606.
(9) Casey, C. P.; Polichnowski, S. W.; Shusterman, A. J .; J ones, C.
R. J . Am. Chem. Soc. 1979, 101, 7282.
S0276-7333(96)00413-X CCC: $12.00 © 1996 American Chemical Society

[2-(Alkenyloxy)ethenyl]carbene Complexes
Organometallics, Vol. 15, No. 22, 1996 4843
Sch em e 1. 2-(Alk en -1-yloxy)eth en yl]ca r ben e
Com p lexes (M ) Cr , W)
to introduce carbohydrates as chiral inductors12 into a
1-metalla-1,3-butadiene. Complexes (CO)5MdC(OEt)Cd
CR(O-acyl) (M ) Cr, W), which contain an enol ester
unit, are quite different in reactivity from corresponding
enol ethers. Such compounds are available (e) by
condensation of methylcarbene complexes with acid
chlorides13,14 and (f) by addition of carboxylic acids to
(1-alkynyl)carbene complexes.15
While pursuing studies on 1-metalla-2,4-dioxy-1,3-
butadienes, we found an access to the new class of
divinyl ether derivatives (E/Z)-(CO)5MdC(OEt)CHdCR-
(O-alkenyl) [M ) Cr, W (A, B)] (Scheme 1) by Michael-
type addition of enolizable carbonyl compounds to an
(1-alkynyl)carbene complex 1a ,b.
F igu r e 1. Molecular structure of the divinyl ether carbene
complex (Z)-3b.
Sch em e 2. C- vs O-Alk en yla tion of 1,3-Dion es w ith
(1-Alk yn yl)ca r ben e Com p lexes (M ) Cr , W)
O-Alken ylation of Car bon yl Com pou n ds. Though
it is well documented that alcohols or phenols yield
Michael-type adducts with an (1-alkynyl)carbene com-
plex, e.g. 1a ,b,12,16,17,24 formation of divinyl ether com-
pounds, e.g. 3a ,b, by O-addition of an enolizable carbo-
nyl compound to a (1-alkynyl)carbene complex has not
been reported before (Scheme 2). Addition of enolizable
1,3-dicarbonyl compounds18,19 or R-aryl ketones1 to 1
was reported to produce pyranylidene complexes result-
ing from ring closure of 1-metalla-1,3,5-trienes, which
are formed as primary C-alkenylation products of the
enolate unit.1,19 We now wish to report that O-alkeny-
lation of cyclic 1,3-dicarbonyl compounds may become
the major reaction path under certain conditions. For
example, addition of catalytic amounts of Et3N to a 1:1
mixture of cyclopentane-1,3-dione (2a ) and (1-alkynyl)-
carbene complex 1a ,b in diethyl ether results in forma-
tion of a (red) divinyl ether derivative 3a ,b and a (blue)
pyranylidene complex 4a ,b in a 3:2 ratio (Scheme 2).
The product ratio of 3:4 is influenced by solvent polarity,
such that e.g. in diethyl ether more O-alkylation product
3 is obtained than in dichloromethane. Since both
compounds, 3 and 4, are unstable in the presence of
base, much attention has to be paid to the reaction time
and the concentration of the catalyst in order to achieve
good chemical yields.
undergo a configurational change to (Z) products in
solution, it can be reasonably assumed that addition of
enolates to 1 would yield a stereoisomer (E)-3 by kinetic
reaction control, which subsequently affords the ther-
modynamically favored isomer (Z)-3. Only (Z) stereoi-
somers of divinyl ethers 3 have been isolated so far. The
configuration of (Z)-3 is assigned on the basis of NOE
enhancements observed between the proton signals of
the vinyl and the phenyl group CHdCPh. More struc-
tural details were obtained from a X-ray analysis of (Z)-
3b (Figure 1, Tables 1 and 2).
The distance between atoms Cr-C4 [2.057(11) Å],
C4-C5 [1.442(15) Å], and C4-O3 [1.323(12) Å] of (Z)-
3b are similar to those observed for (CO)5CrdC(OMe)-
Ph [2.04(3), 1.47(4), and 1.33(2) Å].20 Distance C4-O3
[1.323(12) Å] is much shorter than C6-O7 [1.409(12)
Å] due to the carboxonium character of the former
group. The plane defined by the carbene ligand bisects
the angle between two neighboring carbonyl ligands,
C21-Cr-C4-C5 [44.4(1)°]. Furthermore, the 1-chroma-
Since reaction of phenols 9 with compounds 1 (v.i.)
was shown to initially produce (E) isomers, which
(10) (a) Camps, F.; Llebaria, A.; Moreto´, J . M.; Ricart, S.; Vin˜as, J .
M.; Ros, J .; Ya´n˜ez, R. J . Organomet. Chem. 1991, 401, C17-C19. (b)
Idem. 1992, 440, 79-90.
(11) Duetsch, M.; Stein, F.; Funke, F.; Pohl, E.; Herbst-Irmer, R.;
deMeijere, A. Chem. Ber. 1993, 126, 2535-2541.
(12) Aumann, R. Chem. Ber. 1993, 126, 2773-2778.
(13) Casey, C. P.; Boggs, R. A.; Anderson, R. L. J . Am. Chem. Soc.
1972, 94, 8947-8949.
(14) Aumann, R.; J asper, B.; La¨ge, M.; Krebs, B. Organometallics
1994, 13, 3502-3509.
(15) Aumann, R.; J asper, B.; La¨ge, M.; Krebs, B. Organometallics
1994, 13, 3510-3516.
(16) (a) Camps, F.; Llebaria, A.; Moreto´, J . M.; Ricart, S.; Vin˜as, J .
M.; Ros, J .; Ya´n˜ez, R. J . Organomet. Chem. 1991, 401, C17-C19. (b)
Idem. 1992, 440, 79-90.
(17) Duetsch, M.; Stein, F.; Funke, F.; Pohl, E.; Herbst-Irmer, R.;
deMeijere, A. Chem. Ber. 1993, 126, 2535-2541.
(18) Wang, S. L.; Wulff, W. D. J . Am. Chem. Soc. 1990, 112, 4550-
4552.
(19) Aumann, R.; Roths, K.; J asper, B.; Fro¨hlich, R. Organometallics
1996, 15, 1257-1264.
(20) Mills, O. S.; Redhouse, A. D. J . Chem. Soc. A 1968, 642-647.

4844 Organometallics, Vol. 15, No. 22, 1996
Aumann et al.
Sch em e 3. Dien on e F or m a tion by Novel
F r a gm en ta tion of a Divin yl Eth er Ca r ben e
Com p lex
Ta ble 1. Deta ils of th e X-r a y Cr ysta l Str u ctu r e
An a lysis of (Z)-3b
formula
a (Å)
b (Å)
C21H16CrO8
9.536(1)
35.605(7)
6.144(1)
2086.1(6)
Enraf-Nonius MACH III
223
0.710 73
Pna21 (No. 33)
4
5.93
94.6-99.9
26.33
2321
2321
1342
272
c (Å)
V (Å3)
diffractometer
data coll temp (K)
λ (Å)
space group
Z
µ (cm-1
)
empirical abs corr (%)
θmax (deg)
no. of data collcd
no. of unique data
no. of data obsd (g2σ(I))
no. of refined params
R1 (g2σ(I))
0.061
0.162
0.12(8)
wR2 (g2σ(I))
Flack param
goodness of fit
1.054
program used
SCHAKAL-92
Ta ble 2. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for (Z)-3b
Cr-C(4)
2.057(11)
1.489(18)
1.447(14)
1.323(12)
1.442(15)
1.358(15)
1.409(12)
1.467(15)
O(7)-C(8)
1.373(11)
1.295(16)
1.489(14)
1.452(17)
1.210(17)
1.529(22)
1.469(18)
C(1)-C(2)
C(2)-O(3)
O(3)-C(4)
C(4)-C(5)
C(5)-C(6)
C(6)-O(7)
C(6)-C(61)
C(8)-C(9)
Transformation of compound (Z)-3 into (E/Z)-5 is
assumed to proceed via a homofurane intermediate D,
on the basis of related studies of homopyrroles derived
from alkyne insertion into [(vinylamino)carbene]iron
complexes.21 Homofurans of type D may be generated
as precursors to dienediones also on the interaction of
furans with metal carbenoids generated by Rh2(OAc)4-
catalyzed decomposition of an R-diazo ketone.22 Other
than 1,3-dien-5-one imines,21 cyclization of the 1,3-dien-
5-one unit of compound (E)-5 (to afford a pyrane E) has
not been observed (Scheme 3). The configuration of the
stereoisomers (E/Z)-5 was determined by NOE mea-
surements, which indicate a positive enhancement of
the vinyl signal 2-H on irradiation of OCH2 in stereoi-
somer (E)-5 but not in (Z)-5. Compound (E)-5 could be
isolated by fractionating crystallization and was shown
by 1H NMR spectra to afford a 3:1 mixture of (E/Z)-5 in
solution at 20 °C within several hours.
O-Alk en yla tion of 9-P h en a n th r ol. Both, O- and
C-addition products, 7 (58%) and 8 (28%) are obtained
from reaction of 9-phenanthrol (6) with (1-alkynyl)-
carbene complex 1b in presence of Et3N (Scheme 4).
Compound 7 forms stereoisomers (E)-7 and (Z)-7, both
of which were isolated and fully characterized.
En ol Eth er s 10. Other than enolizable 1,3-carbonyl
compounds 2 or 9-phenanthrol (6), phenols do not afford
C- but O-alkylation products only. (1-Alkynyl)carbene
complexes 1a ,b add phenol (2a ) in presence of catalytic
amounts of Et3N at 0 °C to give enol ethers 10 (Scheme
5). The reaction is initiated by formation of an allenide
complex,23 from which the stereoisomer (E)-10 is ob-
tained through kinetic control of the protonation site.24
Compounds (E)-10 can be isolated in brick-red crystals
C(8)-C(12)
C(9)-C(10)
C(10)-O(10)
C(10)-C(11)
C(11)-C(12)
C(22)-Cr-C(4)
C(24)-Cr-C(4)
C(21)-Cr-C(4)
C(23)-Cr-C(4)
C(25)-Cr-C(4)
174.7(5)
96.0(5)
87.8(5)
94.2(5)
86.1(5)
C(5)-C(6)-C(61)
O(7)-C(6)-C(61)
C(8)-O(7)-C(6)
C(9)-C(8)-O(7)
C(9)-C(8)-C(12)
124.7(10)
114.0(9)
116.8(8)
129.9(10)
115.4(10)
114.7(9)
107.5(11)
125.3(14)
O(3)-C(2)-C(1) 106.9(12) O(7)-C(8)-C(12)
C(4)-O(3)-C(2) 122.4(9)
O(3)-C(4)-C(5) 109.9(9)
O(3)-C(4)-Cr
C(5)-C(4)-Cr
C(6)-C(5)-C(4) 129.0(10) C(12)-C(11)-C(10) 104.6(9)
C(5)-C(6)-O(7) 121.1(9)
C(8)-C(9)-C(10)
O(10)-C(10)-C(9)
130.2(8)
119.9(7)
O(10)-C(10)-C(11) 126.5(12)
C(9)-C(10)-C(11)
108.1(11)
C(11)-C(12)-C(8)
104.0(11)
1,3-diene unit is essentially planar (C4-C5-C6-O7 )
-3.8°) and adopts a transoid configuration [Cr-C4-
C5-C6 ) 154.8(1)°], in which the cycloalkenyloxy group
is almost perpendicular to the adjacent CdC bond [C6-
O7-C8-C9 ) -9.1(1)°, C5-C6-O7-C8 ) 99.8(1)°].
Steric interactions between the cycloalkenyloxy group
and the phenyl and ethoxy substituents appear to force
the cycloalkenyloxy group out of the plane of the
metalladiene. Thus delocalization of electron density
from O7 into the adjacent CdC bond of the 1-chroma-
1,3-diene unit is expected to be smaller than into the
adjacent CdC bond of the cycloalkenyl unit. Bond
angles and bond distances of the O3-C4-C5-C6-O7
backbone are similar to that found for {[2-(acyloxy)-
ethenyl]carbene}pentacarbonyltungsten complexes.14
Dien on es by F r a gm en ta tion . Thermolysis of the
chromium complex (Z)-3b at 80 °C for 2 h does not result
in a Claisen-type O/C-rearrangement but in a novel
fragmentation of the divinyl ether unit to produce a 3:1
mixture of diene diones (E/Z)-5 by elimination of
Cr(CO)6. Interestingly, the overall process involves
insertion of the C3 unit of the (1-alkynyl)carbene
complex 1 into the C,O bond of the carbonyl component
2 (Scheme 3).
(21) Aumann, R.; Trentmann, B.; Kru¨ger, C.; Lutz, F. Chem. Ber.
1991, 124, 2595-2602.
(22) (a) Wenkert, E.; Decorzant, R.; Na¨f, F. Helv. Chim. Acta 1989,
72, 756-766. (b) Wenkert, E. Polyene Synthesis. In New Trends in
Natural Product Chemistry 1986, Studies in Organic Chemistry; Atta-
ur-Rahman, LeQuesne, P. W., Eds.; Elsevier: Amsterdam, 1986; Vol.
26, p 557.
(23) Aumann, R.; J asper, B.; La¨ge, M.; Krebs, B. Chem. Ber. 1994,
127, 2475-2482.
(24) The configurational assignment of the phenol derivative 10b
is different from what has been reported before in refs 16 and 17.

[2-(Alkenyloxy)ethenyl]carbene Complexes
Organometallics, Vol. 15, No. 22, 1996 4845
Ta ble 3. Selected (13C a n d 1H) NMR Sh ifts (δ
Va lu es) a n d ν(CdC) IR F r equ en cies (cm -1) of
Com p ou n d s (E)-10 a n d (Z)-10
Sch em e 4. O- a n d C-Alk en yla tion of 9-P h en a n th r ol
10
M
Ar
δ(MdC) δ(C4) δ(i-C,Ar) δ(3-H) ν(CdC)
(E)-10a
(Z)-10a
(E)-10b Cr Ph
(Z)-10b Cr Ph
W
W
Ph
Ph
300.7
303.8
328.5
331.5
300.7
304.1
328.6
332.1
154.0
148.5
154.1
144.9
151.4
148.3
151.7
144.4
161.0
157.7
157.8
157.0
160.8
155.2
157.2
155.3
7.08
7.65
7.07
7.68
7.07
7.76
7.07
7.74
1552.8
1558.9
1551.7
1558.5
1548.5
1557.2
1552.2
1559.0
(E)-10c
(Z)-10c
W
W
2-napha
2-napha
(E)-10d Cr 2-napha
(Z)-10d Cr 2-napha
a
2-Naphthyl.
Sch em e 5. 1-Meta lla -2,4-d ioxy-1,3-bu ta d ien es 10 by
Mich a el Ad d ition of Ar yloxy Com p ou n d s 9 to
(1-Alk yn yl)ca r ben e Com p lexes
F igu r e 2. Molecular structure of 1-chroma-1,3-diene (E)-
10d .
isolated separately and were shown to be interconverted
to identical (E/Z) mixtures.25
Apart from the different color of crystalline (Z)-10 and
(E)-10, as the most simple means for discrimination of
such isomers, the configurational assignment of com-
pounds 10 is based on NMR and IR data (Table 3). The
carbon signals C4 and i-C Ar in the 13C NMR spectra
of (Z)-10 are characteristically shifted to lower field by
a γ-effect. A strong downfield shift of 0.6-0.7 ppm is
observed also for the hydrogen signal of 3-H in com-
pounds (Z)-10, due to the anisotropic influence of the
neighboring phenyl group. In the IR spectra a slight
hypsochromic shift of the ν(CdC) band seems to be
associated with the (Z) configuration of 10.
As can be seen from the X-ray structure analysis of
compound (E)-10d (Figure 2, Tables 4 and 5), the
1-chroma-1,3-diene unit of this compound is twisted and
exhibits features similar to those of compound (Z)-3b,
exept for the configuration of the CdC bond.
by fractionating crystallization. They exhibit configu-
rational stability in the solid state but undergo facile
(E/Z) isomerization at the CdC(OAr)Ph bond in solu-
tion, which is weakened by polarization of capto-dative
bond system (CO-)5MC(OEt)dCHC(dO+Ar)Ph. An at-
tempt to isolate compounds (E)-10 by chromatography
inevitably results in production of mixtures of (E/Z)-10.
Furthermore, stereoisomers (Z)-10 are more stable than
the corresponding compounds (E)-10 and thus are
accumulated in the mother liquor of the reaction
mixture at 20 °C. Isomers (Z)-10 can be isolated by
crystallization from “enriched” reaction mixtures. They
form dark red crystals, quite different in color and
appearance from those of corresponding isomers (E)-10.
According to NMR measurements mixtures of identical
(E/Z) isomeric ratio are produced in solution at 20 °C
and (more rapidly) at 50 °C from both isomers (E)-10
and (Z)-10. It should be noted that compounds 10
represent one of the up to date rare examples for which
both (E) and (Z) isomers of 1-metalla-1,3-dienes were
Bin u clea r 1-Meta lla -1,3-d ien es. Since bridged bi-
nuclear complexes containing π systems have gained
much interest recently,14,26-29 we have prepared the
binuclear carbene complexes (CO)5MdC(OEt)CHdC-
(Ph)OArO(Ph)CdCH(OEt)CdM(CO)5 (M ) Cr, W) by
(25) Aumann, R.; J asper, B.; Goddard, R.; Kru¨ger, C. Chem. Ber.
1994, 127, 717-724.
(26) For a recent review see: Beck, W.; Niemer, B.; Wieser, M.
Angew. Chem. 1993, 105, 969-996; Angew. Chem., Int. Ed. Engl. 1993,
32, 923-960.

4846 Organometallics, Vol. 15, No. 22, 1996
Aumann et al.
Ta ble 4. Deta ils of th e X-r a y Cr ysta l Str u ctu r e
An a lyses of (E)-10d : Da ta Collection a n d Str u ctu r e
Solu tion a
formula
fw
C26H18CrO7
494.40
cryst system
space group
a (Å)
b (Å)
c (Å)
monoclinic
P21/n (No. 14)
6.365(1)
18.771(2)
19.804(1)
95.32(1)
2355.9(5)
Enraf-Nonius MACH3
223(2)
â (deg)
V (Å3)
diffractometer
temp (K)
λ (Å)
0.710 73
4
Z
F igu r e 3. Molecular structure of binuclear compound
(E,E)-12a .
F(000)
1016
1.394
5.3
93.4-99.7
25.00
4547
4150
Dcalcd (Mg/m3)
µ (cm-1
empirical abs corr (%)
θmax (deg)
no. of data collcd
no. of unique data
Rmerge
)
Sch em e 6. Bin u clea r 1-Meta lla -1,3-d ien es 12
Der ived fr om 1,1′-Bin a p h th ol
0.047
no. of obsd data (g2σ(I))
no. of refined params
R1 (g2σ(I))
3063
308
0.051
0.161
1.104
0.66/-0.61
wR2 (g2σ(I))
2
goodness-of-fit on F
largest diff peak and hole (e Å-3
)
a
Ta ble 6. Cr ysta l Da ta a n d Str u ctu r e An a lysis
Programs used: SHELXS-86, SHELXL-93, and SCHAKAL-
for (E,E)-12a
92.
empirical formula
fw
C52H34O14W2‚2CH2Cl2
1420.34
223(2)
Ta ble 5. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for (E)-10d
temp (K)
wavelength (Å)
cryst system
space group
a (Å)
0.710 73
C(1)-C(5)
O(2)-C(3)
Cr-C(1)
1.458(5)
1.444(4)
2.046(4)
1.322(4)
C(3)-C(4)
C(5)-C(6)
C(6)-O(7)
O(7)-C(8)
1.493(6)
1.342(5)
1.371(4)
1.392(5)
monoclinic
C2/c (No. 15)
27.503(1)
11.948(1)
17.166(1)
106.94(1)
5396.1(6)
4
1.748
2760
4.52
ψ-scan
C(1)-O(2)
b (Å)
c (Å)
O(2)-C(1)-C(5)
O(2)-C(1)-Cr
C(5)-C(1)-Cr
C(1)-O(2)-C(3)
O(2)-C(3)-C(4)
107.5(3)
131.5(3)
121.0(3)
123.4(3)
106.7(3)
C(1)-C(5)-C(6)
C(5)-C(6)-O(7)
C(5)-C(6)-C(61)
O(7)-C(6)-C(61)
C(6)-O(7)-C(8)
124.0(3)
123.3(3)
126.1(3)
110.2(3)
118.7(3)
â (deg)
V (Å3)
Z
calcd density (Mg m-3
F(000)
)
µ (mm-1
abs corr
)
base-catalyzed addition of dihydroxyaryl compounds Ar-
(OH)2 (Ar ) 1,4-phenylene, 1,3-phenylene, 1,1′-binaph-
thyl). Reaction of 2 equiv of 1a ,b with 1,1′-binaphthol
(11) affords compounds 12. Isomers (E,E)-12a ,b are
formed in yields of 88% (12a ) and 85% (12b) (Scheme
θ range (deg)
data collcd
data indepd
2.12-26.30
5660
5468
3597
data obsd [I g 2σ(I)]
refined params
R (all data/obsd)
wR2 (all data/obsd)
361
1
6). According to H NMR measurements, these com-
0.069/0.029
0.118/0.091
1.18/-1.03
Enraf-Nonius MACH3
MolEN, SHELXS86,
SHELXL-93, XP
pounds slowly rearrange in solution and produce mix-
tures of (E/Z)-12 and (Z/Z)-12.
diff Fourier (e Å-3
diffractometer
)
The tungsten complex (E,E)-12a was characterized by
X-ray analysis (Figure 3, Tables 6 and 7) of a crystal
containing 2 molecules of CH2Cl2 per unit. A second
sample of this compound, which has been obtained by
recrystallizing from petroleum ether was also investi-
gated. It was monoclinic, space group P21/n (No. 14),
programs used
with a ) 17.338(2) Å, b ) 9.665(1) Å, c ) 32.168(3) Å,
â ) 102.28(1)°, V ) 5267(1) Å3, and Z ) 4 at ambient
temperature, and contained petroleum ether in a strongly
disordered way, so that a convenient crystal chemical
description of the solvent was not possible even with
constraints. Refinement by neglecting the solvent and
with anisotropic treatment of all non-hydrogen atoms
(hydrogen atoms riding in calculated positions) lead to
R ) 0.055 for 613 parameters against 7097 independent
reflections. Due to the missing part of electron density,
the standard deviations were in the order of the second
digit in the case of bond lengths. Therefore a detailed
discussion of the structure of the hydrocarbon-contain-
ing sample could not be achieved. In this case the
asymmetric unit contains one independent complete
molecule with two metal centers, while in the crystals
(27) (a) Etzenhouser, B. A.; Chen, Q.; Sponsler, M. B. Organome-
tallics 1993, 13, 4176-4178. (b) Rabier, A.; Lugan, N.; Mathieu, R.;
Geoffroy, G. L. Organometallics 1994, 13, 4676-4678. (c) Zhou, Y.;
Seyler, J . W.; Weng, W.; Arif, A. M.; Gladysz, J . A. J . Am. Chem. Soc.
1993, 115, 889-897. (d) Aumann, R.; Heinen, H. Chem. Ber. 1987,
120, 537-540. (e) Tran Huy, N. H.; Lefloch, P.; Robert, F.; J eannin,
Y. J . Organomet. Chem. 1987, 327, 211-221. (f) Neidlein, R.; Gu¨rtler,
S.; Krieger, C. Helv. Chim. Acta 1994, 77, 2303-2322. (g) Fox, H. H.;
Lee, J .-K.; Park, L.-Y.; Schrock, R. R. Organometallics 1993, 12, 759-
768. (h) Heck, J .; Kriebisch, K.-A.; Massa, W.; Wocadlo, S. J . Orga-
nomet. Chem. 1994, 482, 81-84. (i) Albrecht, T.; Sauer, J .; No¨th, H.
Tetrahedron Lett. 1994, 35, 561-564.
(28) Aumann, R.; J asper, B.; Fro¨hlich, R.; Kotila, S. J . Organomet.
Chem. 1995, 502, 137-141.
(29) Aumann, R.; Hinterding, P.; Kru¨ger, C.; Goddard, R. J . Orga-
nomet. Chem. 1993, 459, 145-149.

[2-(Alkenyloxy)ethenyl]carbene Complexes
Organometallics, Vol. 15, No. 22, 1996 4847
Ta ble 7. Selected Bon d Len gth s (Å) a n d An gles
Sch em e 8. (Am in o)k etoca r ben e Com p lex 18 a n d
Acid Am id e 19
(d eg) for (E,E)-12a a
W-C(2)
2.201(5)
1.308(6)
1.445(6)
1.341(6)
1.369(5)
1.401(5)
1.434(6)
1.476(8)
1.374(6)
1.432(6)
C(11)-C(11)1
C(12)-C(13)
C(13)-C(14)
C(14)-C(15)
C(15)-C(16)
C(15)-C(20)
C(16)-C(17)
C(17)-C(18)
C(18)-C(19)
C(19)-C(20)
1.504(9)
1.388(7)
1.364(7)
1.401(7)
1.414(7)
1.438(7)
1.348(8)
1.397(8)
1.368(7)
1.422(7)
C(2)-O(6)
C(2)-C(3)
C(3)-C(4)
C(4)-O(5)
O(5)-C(12)
O(6)-C(7)
C(7)-C(8)
C(11)-C(12)
C(11)-C(20)
O(6)-C(2)-C(3)
O(6)-C(2)-W
108.0(4) C(13)-C(12)-O(5)
115.3(4)
129.8(3) C(14)-C(13)-C(12) 119.4(5)
122.2(4) C(13)-C(14)-C(15) 121.3(5)
126.3(5) C(14)-C(15)-C(16) 122.7(5)
123.4(4) C(14)-C(15)-C(20) 118.8(5)
119.4(4) C(16)-C(15)-C(20) 118.5(5)
123.5(4) C(17)-C(16)-C(15) 121.8(5)
107.5(5) C(16)-C(17)-C(18) 120.2(5)
117.5(4) C(19)-C(18)-C(17) 120.9(6)
C(3)-C(2)-W
C(4)-C(3)-C(2)
C(3)-C(4)-O(5)
C(4)-O(5)-C(12)
C(2)-O(6)-C(7)
O(6)-C(7)-C(8)
C(12)-C(11)-C(20)
goes a ligand exchange of the ketenimine against an
isocyanide ligand. Thus, workup of the reaction mixture
by chromatography affords compounds 18 and 19, which
are expected to be formed by hydrolysis of (E)-20, and
15, respectively (Scheme 8).
C(12)-C(11)-C(11)1 120.9(4) C(18)-C(19)-C(20) 120.8(5)
C(20)-C(11)-C(11)1 121.6(4) C(19)-C(20)-C(11) 122.7(5)
C(11)-C(12)-C(13)
C(11)-C(12)-O(5)
123.5(5) C(19)-C(20)-C(15) 117.8(4)
121.1(4) C(11)-C(20)-C(15) 119.4(4)
Exp er im en ta l Section
All operations were carried out under an atmosphere of
argon. All solvents were dried and distilled prior to use.
Hexane (bp 70 °C) was distilled and stored over sodium wire
prior to use. All 1H (300 MHz) and 13C (75.5 MHz) NMR
spectra were recorded on a Bruker ARX 300 instrument in
CDCl3, unless otherwise indicated, and all chemical shift
values refer to δTMS ) 0.00. 13C NMR multiplicities were
determined by DEPT measurements. NOE, double resonance
spin-decoupling, and low-temperature 1H NMR measurements
were carried out on a Bruker AM 360 instrument. IR spectra
were recorded on a Biorad digilab division FTS-45 FT-IR
spectrophotometer. GC/IR spectra were recorded on a Shi-
madzu GC-14A gas chromatograph coupled to a Biorad digilab
division GC/C32. GC analyses were conducted on a Shimadzu
GC-14A. Elemental analysis were determined on a Perkin-
Elmer 240 elemental analyzer. Analytical TLC plates, Merck
DC-Alufolien Kieselgel 60F240, were viewed by UV light (254
nm) and stained by a 5% aqueous acidic ammonium molybdate
solution. Rf values refer to TLC tests. Chromatographic
purifications were performed on Merck Kieselgel 100. Petro-
leum ether refers to that fraction boiling between 40 and 60
°C.
a
Symmetry transformation used to generate equivalent atoms:
(1) -x, y, -z + 1/2.
Sch em e 7. Bin u clea r 1-Meta lla -1,3-d ien es
14 a n d 16
(3Z)-2-Eth oxy-4-[(3-oxocyclop en t-1-en yl)oxy]-4-p h en -
yl-1,1,1,1,1-p en ta ca r bon yl-1-tu n gsta -1,3-bu ta d ien e (3a )
a n d P en ta ca r bon yl[9-oxo-4-p h en yl-5,6-cyclop en ten o-2H-
p yr a n -2-ylid en e]tu n gsten (4a ). To pentacarbonyl(1-ethoxy-
3-phenyl-2-propyne-1-ylidene)tungsten (1a ) (482 mg, 1.00
mmol) and cyclopentane-1,3-dione (2a ) (118 mg, 1.20 mmol)
in 1 mL of dichloromethane in a 5-mL screwtop vessel is slowly
added triethylamine (20 mg, 0.20 mmol) in 2 mL of dichlo-
romethane with vigorous stirring at 20 °C. Reaction progress
is followed by TLC. After the starting material has been
consumed completely (ca. 1 h at 20 °C), solvent is removed in
vacuo and the residue is dissolved in toluene. Chromatogra-
phy on silica gel with dichloromethane affords blue 4a (203
mg, 38%, Rf ) 0.5 in 1:1 pentane/dichloromethane, blue
crystals from 1:3 dichloromethane/pentane, mp 157 °C), and
elution with dichloromethane/diethyl ether (5:1) yields a red
fraction with 3a (325 mg, 56%, Rf ) 0.5 in dichloromethane,
dark-red crystals from 1:6 dichloromethane/pentane at -15
°C, mp 173 °C).
containing dichloromethane, which data are reported in
Tables 6 and 7, the molecule is built up by symmetry
from one-half; i.e., it contained only one metal center
in the asymmetric unit. Nevertheless, comparision of
both molecules in the two different structures shows no
differences within the observed accuracy.
Br id ged Bin u clea r Ca r ben e Com p lexes 14 a n d
16 were derived from dihydroxyphenylenes 13 and 15
in 76-90%. While compounds (E,E)-14a ,b prove to be
configurationally quite stable, compound (E,E)-16, which
is formed by kinetic reaction control, exhibits a strong
tendency to form the isomer (Z,Z)-16 in solution.
Keten im in e Der iva tives fr om Meta lla d ien e 10b.
Ligand disengagement from Fischer carbene complexes
can be most easily achieved by addition of isocyanides.
The key step of this reaction involves insertion of the
isocyano function into the MdC bond of the carbene
complex, which leads to production of a ketenimine
complex.4b Addition of cyclohexyl isocyanide (17) to the
1-chroma-1,3-diene (E)-10b seems to follow this general
route to a ketenimine complex (E)-20. Depending on
the reaction condition, a small portion of (E)-20 under-
3a . 1H NMR (C6D6): δ 7.48 (1 H, s, 3-H), 7.32 and 6.95 (2:3
H, m each, Ph), 5.20 (1 H, s, OCdCH), 4.41 (2 H, q, OCH2),
2.09 and 2.01 (2 H each, m each, CH2 each), 0.94 (3 H, t,
CH2CH3); 13C NMR (C6D6): δ 305.5 (WdC), 203.9 and 197.5
[trans- and cis-CO, W(CO)5], 202.0 and 186.0 (Cq each, CdO
and dCO), 144.6 (Cq, C4), 132.7 (Cq, i-C Ph), 131.6 (CH, C3);
131.4, 129.5, and 126.9 (1:2:2, CH each, Ph), 109.6 (OCdCH),
80.1 (OCH2), 34.7 and 27.5 (CH2 each), 14.5 (CH2CH3). IR

4848 Organometallics, Vol. 15, No. 22, 1996
Aumann et al.
(diffuse reflection) (cm-1): 2066.2, 1981.7, 1916.6 [ν(CtO)],
1706.1 [ν(CdO)]. IR (hexane): 2067.7 (30), 1978.5 (5), 1941.3
(100) [ν(CtO)]. MS (70 eV) [m/e (%)]: 184W, 580 (20) [M+],
552 (5), 524 (5), 496 (30), 468 (30), 440 (40) [M+ - 5CO], 105
(100). Anal. Calcd for C21H16O8W (580.2): C, 43.47; H, 2.78.
Found: C, 43.62; H, 2.54.
4a . 1H NMR (C6D6): δ 7.98 (1 H, s, 3-H), 7.44 and 7.03 (2:3
H, m each, Ph), 1.82 and 1.70 (2 H each, m each, CH2 each).
13C NMR (C6D6): δ 263.5 (WdC), 204.3 and 198.7 [trans- and
cis-CO, W(CO)5], 196.2 and 192.8 (Cq each, CdO and C6),
142.7 (Cq, C4), 142.0 (CH, C3), 133.3 (Cq, i-C Ph); 131.8, 130.0,
and 128.7 (1:2:2, CH each, Ph), 120.9 (Cq, C5), 33.9 and 25.4
(CH2 each). IR (diffuse reflection) (cm-1): 2060.9 (50), 1979.3
(10), 1913.1 (100) [ν(CtO)], 1722.0 (30) [ν(CdO)]. Anal. Calcd
for C19H10O7W (534.1): C, 42.73; H, 1.89. Found: C, 42.56;
H, 1.81.
(3Z)-2-Eth oxy-4-[(3-oxocyclop en t-1-en yl)oxy]-4-p h en -
yl-1,1,1,1,1-p en t a ca r b on yl-1-ch r om a -1,3-b u t a d ien e (3b )
a n d P en ta ca r bon yl[9-oxo-4-p h en yl-5,6-cyclop en ten o-2H-
p yr a n -2-ylid en e]ch r om iu m (4b). Pentacarbonyl(1-ethoxy-
3-phenyl-2-propyne-1-ylidene)chromium (1b) (350 mg, 1.00
mmol) and cyclopentane-1,3-dione (2a ) (118 mg, 1.20 mmol)
in 1 mL of dichloromethane are reacted with triethylamine
(20 mg, 0.20 mmol) as described above for 2 h at 20 °C.
Chromatography on silica gel with dichloromethane affords
blue 4a (141 mg, 35%, Rf ) 0.5 in 1:1 pentane/dichloromethane,
blue crystals from 1:3 dichloromethane/pentane, mp 132 °C),
and with dichloromethane/diethyl ether (5:1) a red fraction
with 3a is obtained (242 mg, 54%, Rf ) 0.5 in dichloromethane,
dark-red crystals from 1:6 dichloromethane/pentane at -15
°C, mp 162 °C).
mother liquor and can be isolated by fractionating crystalliza-
tion (236 mg, 38%, brown crystals, mp 83 °C).
3c. 1H NMR (C6D6): δ 7.44 (1 H, s, 3-H), 7.34 and 6.95 (2:3
H, m each, Ph), 5.49 (1 H, t, 4J ) 1 Hz, OCdCH), 4.50 (2 H, q,
4
OCH2), 2.08 (2 H, d, J ) 1 Hz, CH2), 1.92 (2 H, s, CH2), 1.08
(3 H, t, CH2CH3), 0.80 [6 H, s, C(CH3)2]. 13C NMR (C6D6): δ
306.1 (WdC), 203.7 and 197.5 [trans- and cis-CO, W(CO)5],
196.0 and 171.8 (Cq each, CdO and dCO), 144.5 and 144.0
(Cq each, C4 and i-C Ph), 132.7 (CH, C3); 131.1, 129.4, and
126.8 (1:2:2, CH each, Ph), 107.2 (Cq, C4a), 80.0 (OCH2), 50.6
(Cq, CMe2), 41.9 and 32.3 (CH2 each, C6 and C8), 28.0
[C(CH3)2], 14.7 (CH2CH3). IR (diffuse reflection) (cm-1): 2066.2,
1981.7, 1916.6 [ν(CtO)], 1706.1 [ν(CdO)]. IR (hexane): 2067.3
(30), 1978.o (5), 1941.1 (100) [ν(CtO)]. Anal. Calcd for
C
24H22O8W (622.3): C, 46.32; H, 3.56. Found: C, 46.38; H,
3.70.
4c. 1H NMR (CDCl3): δ 7.98 (1 H, s, 3-H), 7.50 (3 H, m, m-
und p-H, C6H5), 7.31 (2 H, m, o-H, C6H5), 3.20 (2 H, s, 5-CH2),
2.44 (2 H, s, COCH2), 1.29 [6 H, s, (CH3)2]. 13C NMR (CDCl3):
δ 262.4 (WdC), 204.5 and 198.2 [1:4, trans- and cis-CO,
W(CO)5], 193.8 (Cq, CdO), 181.4 (Cq, C6), 144.9 (CH, C3),
143.6 (Cq, C4), 135.4 (Cq, i-C, C6H5), 130.5-128.4 (CH, C6H5),
128.0 (Cq, C5), 52.7 (COCH2), 43.5 (6-CH2), 32.4 [C(CH3)2)],
28.5 [C(CH3)2]. IR (diffuse reflection) (cm-1): 2062.9, 1971.6,
1929.3, and 1890.5 [ν(CtO)], 1698.0 [ν(CdO)], 1587.5 [ν-
(CdC)]. MS (70 eV) [m/e (%)]: 576 (20) [M+], 436 (20) [M+
-
5CO], 252 (15), 57 (100) [ligand+]. Anal. Calcd for C22H16O7W
(576.2): C, 45.86; H, 2.80. Found: C, 45.91; H, 2.67.
3-(1-E t h o x y -3-o x o -3-p h e n y lp r o p e n y l)c y c lo p e n t -2-
en on e (Z/E-5). (3Z)-1,1,1,1,1-Pentacarbonyl-2-ethoxy-4-(1-
oxycyclopenten-3-one)-4-phenyl-1-chroma-1,3-butadiene (3b)
(112 mg, 0.25 mmol) in 1 mL of C6D6 is heated for 2 h at 80
°C. According to TLC, the starting material has been con-
sumed completely. A white precipitate of Cr(CO)6 is formed,
which is removed by centrifugation. The solution is analyzed
spectroscopically. Addition of pentane affords a yellowish oil,
consisting of a 3:1 mixture of E/Z stereoisomers of 5, from
which white crystals of (E)-5a are obtained after several days
at 0 °C.
3b. 1H NMR (C6D6): δ 7.40 (1 H, s, 3-H), 7.30 and 7.05
(2:3 H, m each, Ph), 5.30 (1 H, s, OCdCH), 4.72 (2 H, q, OCH2),
2.20 and 2.05 (2 H each, m each, CH2 each), 1.05 (3 H, t,
CH2CH3). 13C NMR (C6D6): δ 334.9 (CrdC), 224.5 and 217.0
[trans- and cis-CO, Cr(CO)5], 202.2 and 186.4 (Cq each, CdO
and dCO), 141.6 (Cq, C4), 132.8 (Cq, i-C Ph), 131.0 (CH, C3);
129.8, 127.5, and 126.7 (2:1:2, CH each, Ph), 110.2 (OCdCH),
77.7 (OCH2), 35.0 and 27.9 (CH2 each), 15.0 (CH2CH3). IR
(diffuse reflection) (cm-1): 2059.1, 1982.3, 1939.0 [ν(CtO)],
1705.9 [ν(CdO)]. IR (hexane): 2059.8 (30), 1949.7 (100) [ν-
(E)-5. 1H NMR (C6D6): δ 7.90, 7.19, and 7.05 (2:1:2 H, m
4
each, Ph), 6.39 (1 H, t, J ) 1.7 and 1.7 Hz, 2′-H), 5.70 (1 H,
(CtO)]. MS (70 eV) [m/e (%)]: 448 (20) [M+], 308 (40) [M+
-
s, 2-H), 3.20 (2 H, q, OCH2), 2.51 (2 H, m, 4′-H2), 2.10 (2 H,
5′-H2), 0.95 (3 H, t, CH2CH3). 13C NMR (C6D6): δ 207.2 (Cq,
C3′), 189.0 (Cq, C3), 169.4 and 164.8 (Cq each, C1 and C1′),
139.8 (Cq, i-C, Ph); 134.0, 131.0, 128.4, and 128.2 (2:1:2:1, CH
each, C2′ and Ph), 100.2 (CH, C2), 64.1 (OCH2), 34.9 and 29.8
(CH2 each, C4′ and C5′), 16.0 (CH3). IR (diffuse reflection)
(cm-1): 1707.9 and 1858.8 [ν(CdO) each]. MS (70 eV) [m/e
(%)]: 256 (20) [M+], 228 (60) [M+ - C2H4], 200 (40), 199 (50),
5CO], 52 (100). Anal. Calcd for C21H16CrO8 (448.4): C, 56.26;
H, 3.60. Found: C, 56.16; H, 3.54.
4b. 1H NMR (C6D6): δ 7.82 (1 H, s, 3-H), 7.24 and 6.85
(2:3 H, m each, Ph), 1.70 and 1.61 (2 H each, m each, CH2
each). 13C NMR (C6D6): δ 290.8 (CrdC), 224.5 and 217.5
[trans- and cis-CO, Cr(CO)5], 196.2 and 193.6 (Cq each, CdO
and C6), 139.3 (CH, C3), 139.0 (Cq, C4), 132.0 (Cq, i-C Ph);
131.7, 130.4, and 129.1 (1:2:2, CH each, Ph), 120.5 (Cq, C5),
34.0 and 25.4 (CH2 each). IR (diffuse reflection) (cm-1):
2053.5, 1984.3, 1925.1 [ν(CtO)], 1721.8 [ν(CdO)]. IR (hex-
ane): 2055.4 (30), 1988.1 (5), 1952.0 (100) [ν(CtO)]. MS (70
eV) [m/e (%)]: 402 (40) [M+], 374 (10), 346 (20), 318 (40), 290
184 (60), 105 (80), 77 (100). Anal. Calcd for
C16H16O3
(256.3): C, 74.98; H, 6.29. Found: C, 75.16; H, 6.46.
(Z)-5. 1H NMR (C6D6): δ 7.96, 7.02, and 6.94 (2:1:2 H, m
4
each, Ph), 6.52 (1 H, t, J ) 1.7 and 1.7 Hz, 2′-H), 5.94 (1 H,
s, 2-H), 3.90 (2 H, q, OCH2), 1.98 (2 H, m, 4′-H2), 1.82 (2 H,
(40), 262 (40) [M+ - 5CO], 52 (100). Anal. Calcd for C19H10
-
5′-H
2), 0.93 (3 H, t, CH2CH3). 13C NMR (C6D6): δ 206.8 (Cq,
CrO7 (402.3): C, 56.76; H, 2.51. Found: C, 56.56; H, 2.46.
(3Z)-2-Eth oxy-4-[(5,5-d im eth yl-3-oxocycloh ex-1-en yl)-
oxy]-4-ph en yl-1,1,1,1,1-pen tacar bon yl-1-tu n gsta-1,3-bu ta-
d ien e (3c) a n d P en ta ca r bon yl(7,7-d im eth yl-4-p h en yl-6,8-
d ih yd r o-2H-ch r om en e-5-on e-2-ylid en e)tu n gsten (4c). To
pentacarbonyl(1-ethoxy-3-phenyl-2-propyne-1-ylidene)tung-
sten (1a ) (482 mg, 1.00 mmol) and 5,5-dimethylcyclohexane-
1,3-dione (2b) (150 mg, 1.00 mmol) in a 5-mL screw-top vessel
is added a solution of triethylamine (101 mg, 1.00 mmol) in 2
mL of diethyl ether. The mixture is shaken immediately for
3 min to give a violet precipitate in a slightly exothermic
reaction. Pentane (2 mL) is added after 5 min at 20 °C, and
the mixture is homogenized by ultrasonic irradiation for 10
min. According to a TLC, starting material is consumed
completely. Centrifugation affords violet crystals of 4c (299
mg, 52%, Rf ) 0.7 in dichloromethane, mp 159 °C from 1:1
diethyl ether/pentane). Compound 3c is accumulated in the
C3′), 190.1 (Cq, C3), 168.2 and 162.9 (Cq each, C1 and C1′),
139.0 (Cq, i-C, Ph); 132.9, 131.0, 128.6, and 128.0 (2:1:1:2:1,
CH each, C2′ and Ph), 106.4 (CH, C2), 70.0 (OCH2), 35.0 and
26.6 (CH2 each, C4′ and C5′), 16.7 (CH3). IR (diffuse reflection)
(cm-1): 1707.9 and 1858.8 [ν(CdO) each]. MS (70 eV) [m/e
(%)]: 256 (20) [M+], 228 (60) [M+ - C2H4], 200 (40), 199 (50),
184 (60), 105 (80), 77 (100).
2-E t h oxy-4-(9-p h en a n t h r oxy)-4-p h en yl-1,1,1,1,1-p en -
ta ca r bon yl-1-tu n gsta -1,3-bu ta d ien e [(E/Z)-7] a n d P en -
tacar bon yl(4-ph en yl-2H-1-oxatr iph en ylen -2-yliden e)tu n g-
sten (8). To pentacarbonyl(1-ethoxy-3-phenyl-2-propyne-1-
ylidene)tungsten (1a ) (241 mg, 0.50 mmol) and 9-phenanthrol
(6) (97 mg, 0.50 mmol) in a 5-mL screw-top vessel is added a
solution of triethylamine (0.51 mg, 0.50 mmol) in 2 mL of
diethyl ether. The mixture is shaken immediately for 3 min
to give a dark red solution initially, from which a dark brown
solid begins to precipitate in a slightly exothermic reaction.

[2-(Alkenyloxy)ethenyl]carbene Complexes
Organometallics, Vol. 15, No. 22, 1996 4849
According to TLC (in 4:1 pentane/dichloromethane) starting
material (Rf ) 0.8) is consumed completely after 3-4 min.
Pentane (2 mL) is added to the mother liquor after 5 min at
20 °C, and the solid (ca. 280 mg) is removed by centrifugation
after 10 min. Extraction with 5 mL of diethyl ether at 20 °C
leaves a violet residue of compound 8 (84 mg, 28%, mp 60 °C).
Concentration of the ether extract to 1 mL and addition of 3
mL of pentane affords essentially clean compound (E)-7 (196
mg, 58%, Rf ) 0.6 in 4:1 pentane/dichloromethane, mp 110
°C). A TLC of the mother liquor indicates the presence of
bright-brown (Z)-7 (Rf ) 0.7 in 4:1 pentane/dichloromethane),
together with traces of dark-brown (E)-7 (Rf ) 0.6) and of some
violet compound 8 (Rf ) 0.5). Compound (Z)-7 is generated
by thermal isomerization of (E)-7 and is accumulated in the
mother liquor from which it can be isolated by fractionating
crystallization at -78 °C (52 mg, 15%, mp 81 °C). Thermal
isomerization of either (E)-7 or (Z)-7 at 50 °C affords an isomer
mixture of (E/Z) ) 1:3.
added triethylamine (50 mg, 0.50 mmol) in 3 mL of pentane
with stirring at 0 °C. A gradual change of color from brown
to red is observed, and formation of a red compound 10a can
be followed by TLC (Rf ) 0.5 in pentane). Starting material
is consumed completely after 3-4 h at 0 °C, while a 10:1
mixture of (E/Z)-10a is formed initially (1H NMR analysis in
C6D6 at 10 °C). Bright red crystals of (E)-10a (mp 75 °C) are
obtained by crystallization at -15 °C. Workup by chroma-
tography on silica gel (20 × 2 cm column) with pentane/
dichloromethane (5:1 to 3:1) affords a red fraction of isomer
ratio (E/Z)-10a ) 1:3 (1H NMR analysis) (404 mg, 91%, red
oil). An identical isomer ratio (E/Z)-10a ) 1:3 is achieved in
a solution of isomerically pure (E)-10a at 50 °C after 3 h.
Fractionating crystallization of the (E/Z)-10a ) 1:3 mixture
from pentane at -15 °C affords dark red crystals of (Z)-10a ,
mp 75 °C.
(E)-10a . 1H NMR (C6D6): δ 7.26 and 7.03 (2:3 H, m each,
4-Ph), 6.90, 6.75, and 6.65 (2:2:1 H, m each, 4-phenoxy), 7.08
(1 H, s, 3-H), 4.36 (2 H, q, OCH2), 0.55 (3 H, t, CH3). 13C NMR
(C6D6): δ 300.7 (WdC), 203.9 and 198.0 [1:4, trans- and cis-
CO, W(CO)5], 161.0 (Cq, i-C, phenoxy), 154.0 (C4), 135.8 (Cq,
i-C, 4-Ph), 130.4 (CH, C3); 130.3, 129.6, and 128.1 (2:2:1, CH
each, 4-Ph); 129.2, 121.4, and 115.7 (2:1:2, CH each, phenoxy);
78.6 (OCH2), 13.6 (CH3). IR (hexane) (cm-1) (%): ν ) 2064.7
(30), 1982.8 (5), 1942.2 (100) [ν(CtO)]; 1552.8 (20) [ν(CdC)].
MS (70 eV), 184W [m/e (%)]: 576 (20) [M+], 548 (30), 492 (60),
464 (40), 436 (70) [M+ - 5CO], 377 (100), 351 (95), 324 (100).
(E)-7. 1H NMR (C6D6): δ 8.43, 8.38, 8.16, and 7.60 (1 H
each, m each, 1′-, 4′-, 5′-, and 8′-H, phenanth); 8.12 (1 H, s,
3-H), 7.52 and 7.03 (2:3 H, m each, 4-Ph); 7.41, 7.38, 7.35, and
7.18 (1 H each, m each, 2′-, 3′-, 6′-, and 7′-H, phenanth); 7.08
(1 H, s, 10′-H, phenanth), 4.23 (2 H, q, OCH2), 0.56 (3 H, t,
CH3). 13C NMR (C6D6): δ 301.6 (WdC), 203.7 and 197.8 [1:4,
trans- and cis-CO, W(CO)5], 159.6 (Cq, C-9, phenanth), 148.3
(Cq, C4), 135.6 (Cq, i-C, 4-Ph), 130.1, 129.8, and 128.2 (2:2:1,
CH each, 4-Ph); 130.2-123.5 (CH each, C3, C-2′-C-4′ and
C-5′-C-8′, phenanth), 131.3, 131.0, 126.5, and 124.3 (Cq each,
C-10a′, C-4a′, C-4b′ and C-8a′, phenanth); 117.6 (CH, C-10′,
phenanth), 78.6 (OCH2), 13.6 (CH3). IR (hexane) (cm-1) (%):
ν ) 2064.7 (30), 1982.8 (5), 1940.2 (100) [ν(CtO)]; 1553.6 (20)
[ν(CdC)]. MS (70 eV), 184W [m/e (%)]: 676 (20) [M+], 648 (20),
620 (5), 592 (40), 536 (40) [M+ - 5CO], 478 (50), 352 (40), 289
(60), 69 (100). Anal. Calcd for C30H20O7W (676.3): C, 53.28;
H, 2.98. Found: C, 53.20; H, 3.10.
Anal. Calcd for
C22H16O7W (576.2): C, 45.86; H, 2.80.
Found: C, 45.66; H, 2.73.
(Z)-10a . 1H NMR (C6D6): δ 7.65 (1 H, s, 3-H), 7.53 and
6.90 (2:3 H, m each, 4-Ph); 6.90, 6.75, and 6.66 (2:2:1 H, m
each, 4-phenoxy), 4.32 (2 H, q, OCH2), 0.83 (3 H, t, CH3). 13C
NMR (C6D6): δ 303.8 (WdC), 203.8 and 197.9 [1:4, trans- and
cis-CO, W(CO)5], 157.7 (Cq, i-C, phenoxy), 148.5 (C4), 134.4
(Cq, i-C, 4-Ph), 131.2 (CH, C3); 130.9, 129.6, and 128.1 (2:2:1,
CH each, 4-Ph); 129.0, 122.7, and 116.3 (2:1:2, CH each,
phenoxy); 79.7 (OCH2), 14.3 (CH3). IR (hexane) (cm-1) (%): ν
) 2064.8 (30), 1982.9 (5), 1943.5 (100) [ν(CtO)]; 1558.9 (20)
[ν(CdC)]. MS (70 eV), 184W [m/e (%)]: 576 (10) [M+], 548 (20),
492 (60), 464 (50), 436 (80) [M+ - 5CO], 377 (100). Anal.
Calcd for C22H16O7W (576.2): C, 45.86; H, 2.80. Found: C,
45.91; H, 2.62.
(Z)-7. 1H NMR (C6D6): δ 8.43, 8.41, 8.30, and 7.40 (1 H
each, “d” each, 1′-, 4′-, 5′-, and 8′-H, phenanth); 7.95 (1 H, s,
3-H), 7.70 and 6.88 (2:3 H, m each, 4-Ph); 7.45, 7.43, 7.25, and
7.21 (1 H each, “t” each, 2′-, 3′-, 6′-, and 7′-H, phenanth); 7.02
(1 H, s, 10′-H, phenanth), 4.10 (2 H, q, OCH2), 0.43 (3 H, t,
CH3). 13C NMR (C6D6): δ 303.9 (WdC), 203.7 and 197.8 [1:4,
trans- and cis-CO, W(CO)5], 151.5 (Cq, C-9, phenanth), 147.6
(Cq, C4), 134.2 (Cq, i-C, 4-Ph); 132.3, 131.4, 125.5, and 122.7
(Cq each, C-10a′, C-4a′, C-4b′, and C-8a′, phenanth); 132.2 (CH,
C3); 130.9, 129.5, and 128.1 (2:2:1, CH each, 4-Ph); 132.1-
122.6 (8 CH, C-2′-C-4′ and C-5′-C-8′, phenanth); 107.5 (CH,
2-Eth oxy-4-p h en yl-4-p h en oxy-1,1,1,1,1-p en ta ca r bon yl-
1-ch r om a -1,3-bu ta d ien e [(Z)-10b a n d (E)-10b]. Pentacar-
bonyl(1-ethoxy-3-phenyl-2-propynylidene)chromium (1b) (482
mg, 1.00 mmol) and phenol (9a ) (94 mg, 1.00 mmol) are reacted
as described above for 3-4 h at 0 °C to afford an (E/Z) ) 10:1
mixture of 10b, which is isomerized to an (E/Z) ) 3:2 mixture
at 50 °C for 3 h. Chromatography on silica gel yields an (E/Z)
) 3:2 mixture (466, 81%, red oil). Fractionating crystallization
from pentane at -15 °C yields dark red crystals of (Z)-10b,
mp 74 °C, and bright red crystals of (E)-10b, mp 87 °C.
(E)-10b. 1H NMR (C6D6): δ 7.29 and 7.05 (2:3 H, m each,
4-Ph), 7.09, 6.92, and 6.88 (2:2:1 H, m each, 4-phenoxy), 7.07
(1 H, s, 3-H), 4.36 (2 H, q, OCH2), 0.55 (3 H, t, CH3). 13C NMR
(C6D6): δ 328.5 (CrdC), 224.2 and 217.4 [1:4, trans- and cis-
CO, Cr(CO)5], 157.8 (Cq, i-C, phenoxy), 154.1 (C4), 135.7 (Cq,
i-C, 4-Ph), 130.1 (CH, C3); 129.8, 128.6, and 126.5 (2:2:1, CH
each, 4-Ph); 129.0, 121.7, and 116.1 (2:1:2, CH each, phenoxy);
76.0 (OCH2), 14.2 (CH3). IR (hexane) (cm-1) (%): ν ) 2056.0
(30), 1943.7 (100) [ν(CtO)]; 1551.5 (20) [ν(CdC)]. MS (70 eV)
[m/e (%)]: 444 (10) [M+], 416 (10), 388 (5) 360 (60), 332 (30),
304 (60) [M+ - 5CO], 276 (60), 275 (40), 260 (60), 145 (80), 52
(100). Anal. Calcd for C22H16CrO7 (444.4): C, 59.47; H, 3.63.
Found: C, 59.64; H, 3.66.
C-10′, phenanth), 80.0 (OCH2), 14.0 (CH3). IR (hexane) (cm-1
)
(%): ν ) 2065.3 (30), 1979.2 (5), 1941.4 (100) [ν(CtO)]; 1554.4
(20) [ν(CdC)]. MS (70 eV), 184W [m/e (%)]: 676 (10) [M+], 648
(30), 620 (0), 592 (80), 536 (80) [M+ - 5CO], 449 (90), 352 (90),
294 (100), 266 (95). Anal. Calcd for C30H20O7W (676.3): C,
53.28; H, 2.98. Found: C, 53.16; H, 3.05.
8. 1H NMR (CDCl3): δ 9.18, 8.86, 7.96 and 7.60 (1 H each,
“d” each, 1′-, 4′-, 5′-, and 8′-H, phenanth); 8.28 (1 H, s, 3-H);
8.00, 7.92, 7.65, and 7.21 (1 H each, “d” each, 2′-, 3′-, 6′-, and
7′-H, phenanth), 7.53 (5 H, m, 4-Ph). 13C NMR (CDCl3): δ
254.6 (WdC), 204.1 and 198.4 [1:4, trans- and cis-CO, W(CO)5],
162.8 (Cq, C-9′, phenanth), 144.5 (Cq, C4), 143.9 (CH, C3),
138.9 (Cq, i-C, C6H5); 132.5, 126.4, 123.3, and 116.6 (Cq each,
C-10a′, C-4a′, C-4b′ and C-8a′, phenanth); 131.4, 129.7, 129.3,
129.2, 128.4, 127.9, 127.8, 127.7, 127.6, 127.3, 123.9, 123.2,
122.8 (CH each; C-2′-C-4′ and C-5′-C-8′, phenanth; diaste-
reotopic C-2′′-C-6′′ 4-Ph). IR (hexane) (cm-1): 2060.0 (30),
1933.8 (100) [ν(CtO)]. MS (70 eV) [m/e (%)]: 630 (20) [M+],
602 (10), 546 (60), 490 (100) [M+ - 5CO], 462 (40), 434 (30).
(Z)-10b. 1H NMR (C6D6): δ 7.68 (1 H, s, 3-H), 7.53 and
6.90 (2:3 H, m each, 4-Ph); 6.88, 6.79, and 6.67 (2:2:1 H, m
each, 4-phenoxy), 4.49 (2 H, q, OCH2), 0.87 (3 H, t, CH3). 13C
NMR (C6D6): δ 331.5 (CrdC), 224.4 and 217.2 [1:4, trans- and
cis-CO, Cr(CO)5], 157.0 (Cq, i-C, phenoxy), 144.9 (C4), 134.3
(Cq, i-C, 4-Ph), 131.1 (CH, C3); 130.2, 128.4, and 127.9 (2:2:1,
CH each, 4-Ph); 129.4, 123.2, and 116.8 (2:1:2, CH each,
Anal. Calcd for
C28H14O6W (630.3): C, 53.36; H, 2.24.
Found: C, 53.64; H, 2.46.
2-Eth oxy-4-p h en yl-4-p h en oxy-1,1,1,1,1-p en ta ca r bon yl-
1-tu n gsta -1,3-bu ta d ien e [(E)-10a a n d (Z)-10a ]. To pen-
tacarbonyl(1-ethoxy-3-phenyl-2-propynylidene)tungsten (1a )
(482 mg, 1.00 mmol) and phenol (9a ) (94 mg, 1.00 mmol) in
0.3 mL of diethyl ether in a 5-mL airtight screw-top vessel is

4850 Organometallics, Vol. 15, No. 22, 1996
Aumann et al.
phenoxy); 77.2 (OCH2), 14.6 (CH3). IR (hexane) (cm-1) (%): ν
) 2056.5 (30), 1979.9 (5), 1945.8 (100) [ν(CtO)]; 1558.5 (20)
[ν(CdC)]. MS (70 eV) [m/e (%)]: 444 (20) [M+], 416 (30), 388
(20) 360 (40), 332 (30), 304 (30) [M+ - 5CO], 276 (50), 145
(80), 52 (100). Anal. Calcd for C22H16CrO7 (444.4): C, 59.47;
H, 3.63. Found: C, 59.66; H, 3.54.
128.6, 127.2, 127.1, 124.9, 117.8, and 111.6 (CH each, C4′, C5′,
C7′, C8′, C6′, C3′, C1′), 77.5 (OCH2), 15.0 (CH3). IR (hexane)
(cm-1) (%): ν ) 2056.7 (30), 1979.9 (5), 1946.0 (100) [ν(CtO)];
1559.0 (20) [ν(CdC)]. MS (70 eV) [m/e (%)]: 494 (20) [M+],
466 (30), 438 (10) 410 (40), 372 (30), 354 (30) [M+ - 5CO], 326
(50), 310 (40), 52 (100). Anal. Calcd for C26H18CrO7 (494.4):
C, 63.16; H, 3.67. Found: C, 63.32; H, 3.52.
(E)-10d . 1H NMR (C6D6): δ 7.60 (3 H, m, napht), 7.30 (1
H, d, 1′-H), 7.20 and 7.10 (2:3 H, m each, 4-Ph); 7.15 (4 H, m,
napht), 7.07 (1 H, s, 3-H), 4.32 (2 H, q, OCH2), 0.56 (3 H, t,
CH3). 13C NMR (C6D6): δ 328.6 (CrdC), 224.2 and 217.1 [1:4,
trans- and cis-CO, Cr(CO)5], 157.2 (Cq, C2′), 151.7 (C4); 135.6,
131.6, and 130.3 (Cq each; C9′, C10′, and i-C 4-Ph), 130.7 (CH,
C3); 130.1, 128.3, and 128.0 (2:2:1, CH each, 4-Ph); 128.5,
128.1, 127.2, 126.1, 125.4, 120.6, and 118.3 (CH each, C4′, C5′,
C7′, C8′, C6′, C3′, C1′), 76.0 (OCH2), 13.8 (CH3). IR (hexane)
(cm-1) (%): ν ) 2056.7 (30), 1979.9 (5), 1946.0 (100) [ν(CtO)];
1552.2 (20) [ν(CdC)]. Anal. Calcd for C26H18CrO7 (494.4): C,
63.16; H, 3.67. Found: C, 63.09; H, 3.66.
2-Eth oxy-4-(n aph th alen -2-yloxy)-4-ph en yl-1,1,1,1,1-pen -
ta ca r bon yl-1-tu n gsta -1,3-bu ta d ien e [(Z)-10c a n d (E)-10c].
Pentacarbonyl(1-ethoxy-3-phenyl-2-propynylidene)tungsten (1a)
(482 mg, 1.00 mmol) and 2-naphthol (9b) (144 mg, 1.00 mmol)
are reacted as described above. A dark brown solution is
obtained initially from which brick red crystals of (E)-10c begin
to precipitate at 20 °C after 30 min (bright red crystals from
diethyl ether/pentane at -15 °C). Starting material is con-
sumed completely after 3-4 h at 20 °C, while an 8:1 mixture
of (E/Z)-10c is formed (1H NMR analysis at 10 °C). At 50 °C
after 3 h a 2:5 mixture of (E/Z)-10c is obtained, from which
(Z)-10c is isolated by fractional crystallization at -15 °C (black
needles). Workup by chromatography on silica gel (20 × 2 cm
column) with pentane/dichloromethane (5:1 to 3:1) affords a
red fraction with an (E/Z) ) 2:5 mixture of 10c (Rf ) 0.5, 5:1
pentane/dichloromethane, total yield 532 mg, 85%).
(E)-10c. 1H NMR (C6D6): δ 7.53 (3 H, m, napht), 7.38 and
7.03 (2:3 H, m each, 4-Ph); 7.20 and 7.10 (3:1 H, m each,
napht), 7.07 (1 H, s, 3-H), 4.22 (2 H, q, OCH2), 0.53 (3 H, t,
CH3). 13C NMR (C6D6): δ 300.7 (WdC), 203.9 and 197.9 [1:4,
trans- and cis-CO, W(CO)5], 160.8 (Cq, C2′), 151.4 (C4); 135.8,
134.5, and 129.9 (Cq each; C9′, C10′, and i-C 4-Ph), 130.9 (CH,
C3); 129.3, 128.0, and 127.8 (2:2:1, CH each, 4-Ph); 128.7,
128.1, 127.2, 126.0, 125.9, 120.4, and 118.2 (CH each, C4′, C5′,
C7′, C8′, C6′, C3′, C1′), 78.2 (OCH2), 13.2 (CH3). IR (hexane)
(cm-1) (%): ν ) 2064.4 (30), 1982.2 (5), 1941.2 (100) [ν(CtO)];
1548.4 (20) [ν(CdC)]. MS (70 eV), 184W [m/e (%)]: 626 (20)
[M+], 598 (60), 542 (60), 414 (40), 486 (70) [M+ - 5CO], 429
(100). Anal. Calcd for C26H18O7W (626.3): C, 49.86; H, 2.90.
Found: C, 48.99; H, 2.93.
(Z)-10c. 1H NMR (C6D6): δ 7.76 (1 H, s, 3-H), 7.49 (3 H,
m, napht), 7.64 and 6.83 (2:3 H, m each, 4-Ph); 7.45, 3.39, and
7.35 (1 H each, d each, 4′-H, 5′-H, and 8′-H), 7.19 (1 H, d, 1′-
H), 7.10-7.00 (3 H, m, 3′-H, 6′-H, and 7′-H), 4.18 (2 H, q,
OCH2), 0.74 (3 H, t, CH3). 13C NMR (C6D6): δ 304.1 (WdC),
203.0 and 197.2 [1:4, trans- and cis-CO, W(CO)5], 155.2 (Cq,
C2′), 148.3 (C4); 134.5, 134.3, and 129.2 (Cq each; C9′, C10′,
and i-C 4-Ph), 131.2 (CH, C3); 130.7, 128.5, and 127.4 (2:2:1,
CH each, 4-Ph); 128.5, 128.3, 127.9, 127.1, 124.9, 117.8, and
111.5 (CH each, C4′, C5′, C7′, C8′, C6′, C3′, C1′), 79.7 (OCH2),
14.3 (CH3). IR (hexane) (cm-1) (%): ν ) 2064.2 (30), 1981.9
(5), 1940.3 (100) [ν(CtO)]; 1557.2 (20) [ν(CdC)]. MS (70 eV),
184W [m/e (%)]: 626 (20) [M+], 598 (60), 542 (60), 414 (30), 486
(70) [M+ - 5CO], 427 (100). Anal. Calcd for C26H18O7W
(626.3): C, 49.86; H, 2.90. Found: C, 48.89; H, 3.03.
2-Eth oxy-4-(n aph th alen -2-yloxy)-4-ph en yl-1,1,1,1,1-pen -
t a ca r b on yl-1-ch r om a -1,3-b u t a d ien e [(Z)-10d a n d (E)-
10d ]. Pentacarbonyl(1-ethoxy-3-phenyl-2-propynylidene)chro-
mium (1b) (350 mg, 1.00 mmol) and 2-naphthol (9a ) (144 mg,
1.00 mmol) are reacted as described above. After 3-4 h at 20
°C a 6:1 mixture of (E/Z)-10d is formed (1H NMR analysis at
10 °C). (E)-10d is isolated by fractionating crystallization at
-15 °C as brick-red crystals, mp 89 °C. At 50 °C after 3 h an
(E/Z) ) 2:3 mixture is obtained, from which (Z)-10d is isolated
by fractionating crystallization at -15 °C (black needles, mp
96 °C). Workup by (rapid) chromatography on silica gel (20
× 2 cm column) with pentane/dichloromethane (5:1 to 3:1)
affords a red fraction with an (E/Z) ) 2:3 mixture of 10d (Rf
) 0.5, 5:1 pentane/dichloromethane, total yield 430 mg, 87%).
(Z)-10d . 1H NMR (C6D6): δ 7.74 (1 H, s, 3-H), 7.60 and
6.90 (2:3 H, m each, 4-Ph); 7.45, 7.40, 7.21, 7.14, and 7.08 (1:
2:1:2:1 H, m each, napht), 4.42 (2 H, q, OCH2), 0.80 (3 H, t,
CH3). 13C NMR (C6D6): δ 332.1 (CrdC), 224.7 and 217.5 [1:4,
trans- and cis-CO, Cr(CO)5], 155.3 (Cq, C2′), 144.4 (C4); 134.6,
134.2, and 130.3 (Cq each; C9′, C10′, and i-C 4-Ph), 130.9 (CH,
C3); 129.4, 128.7, and 128.5 (2:1:1, CH each, 4-Ph); 129.9,
2,2′-Bis(2-et h oxy-4-p h en yl-1,1,1,1,1-p en t a ca r b on yl-1-
tu n gsta -1,3-bu ta d ien -4-yloxy)-1,1′-bin a p h th a len yl [(E,E)-
12a ]. Pentacarbonyl(1-ethoxy-3-phenyl-2-propynylidene)tung-
sten (1a ) (482 mg, 1.00 mmol) and 1,1′-binaphth-2-ol (11) (143
mg, 0.50 mmol) are reacted as described above. Fractionating
crystallization affords brick-red crystals of (E,E)-12a (Rf )
0.4, 5:1 pentane/dichloromethane, 434 mg, 88%). 1H NMR
(C6D6): δ 7.65 and 7.38 (1:1 H, d each, 3J ) 9 Hz, 3′-H and
3
4′H), 7.51 and 7.45 (1:1 H, dd each, J ) 6.5 and 2 Hz each,
5′-H and 8′-H), 7.22 and 7.16 (1:1 H, t each, 6′-H and 7′-H),
6.93 (1 H, s, 3-H), 6.88 and 6.82 (2:3 H, m each, 4-Ph), 3.92
and 3.87 (1 H each, m each, diastereotopic OCH2), 0.26 (3 H,
t, CH3). 13C NMR (C6D6): δ 300.4 (WdC), 203.7 and 197.9
[1:4, trans- and cis-CO, W(CO)5], 160.7 (Cq, C2′), 152.1 (C4);
135.8, 134.3, 132.2, and 129.8 (Cq each; C9′, C10′, C2′, and
i-C 4-Ph), 129.9 (CH, C3); 129.3, 128.0, and 127.7 (2:2:1, CH
each, 4-Ph); 128.6, 128.1, 127.1, 126.0, 125.9, and 120.2 (CH
each, C4′, C5′, C7′, C8′, C6′, C3′), 78.0 (OCH2), 13.3 (CH3). IR
(hexane) (cm-1) (%): ν ) 2064.6 (20), 1983.2 (5), 1941.8 (100)
[ν(CtO)]; 1548.5 (20) [ν(CdC)]. Anal. Calcd for C52H34O14W2
(1250.5): C, 49.94; H, 2.74. Found: C, 49.92; H, 2.81.
2,2′-Bis(2-et h oxy-4-p h en yl-1,1,1,1,1-p en t a ca r b on yl-1-
ch r om a -1,3-bu ta d ien -4-yloxy)-1,1′-bin a p h th a len yl [(E,E)-
12b]. Pentacarbonyl(1-ethoxy-3-phenyl-2-propynylidene)chro-
mium (1b) (350 mg, 1.00 mmol) and 1,1′-binaphth-2-ol (11)
(143 mg, 0.50 mmol) are reacted as described above. After
3-4 h at 20 °C the starting material is consumed completely.
Fractionating crystallization at -15 °C affords brick-red
crystals of (E,E)-12b (Rf ) 0.4, 5:1 pentane/dichloromethane,
419 mg, 85%). 1H NMR (C6D6): δ 7.65 and 7.42 (1:1 H, d each,
3
3J ) 9 Hz, 3′-H and 4′H), 7.50 and 7.42 (1:1 H, dd each, J )
6.5 and 2 Hz each, 5′-H and 8′-H), 7.20 and 7.15 (1:1 H, t each,
6′-H and 7′-H), 6.99 (1 H, s, 3-H), 6.95 and 6.85 (2:3 H, m each,
4-Ph), 3.90 (2 H, m, diastereotopic OCH2), 0.28 (3 H, t, CH3).
13C NMR (C6D6): δ 328.7 (CrdC), 224.1 and 217.4 [1:4, trans-
and cis-CO, Cr(CO)5], 156.3 (Cq, C2′), 150.3 (C4); 135.6, 134.0,
and 131.2 (Cq each, C9′, C10′, and i-C 4-Ph); 131.2 (CH, C3);
129.8, 128.7, and 128.5 (2:2:1, CH each, 4-Ph); 130.7, 129.0,
127.8, 127.1, 125.3 (CH each; C4′, C5′, C6′, C7′, C8′); 123.7
(Cq, C1′), 121.7 (CH, C3′), 75.8 (OCH2), 13.5 (CH3). IR
(hexane) (cm-1) (%): ν ) 2056.4 (30), 1979.8 (5), 1945.1 (100)
[ν(CtO)]; 1553.0 (20) [ν(CdC)]. Anal. Calcd for C52H34Cr2O14
(986.8): C, 63.29; H, 3.47. Found: C, 63.45; H, 3.64.
µ-(1,4-P h en ylen e)bis[(2-eth oxy-4-p h en yl-1,1,1,1,1-p en -
ta ca r bon yl-1-tu n gsta -1,3-bu ta d ien -4-yl)oxy] [(E,E)-14a ].
To pentacarbonyl(1-ethoxy-3-phenyl-2-propynylidene)tungsten
(1a ) (482 mg, 1.00 mmol) and 1,4-dihydroxybenzene (13) (55
mg, 0.50 mmol) in 2.5 mL of diethyl ether in a 5-mL airtight
screw-top vessel is added triethylamine (50 mg, 0.50 mmol)
in 1.5 mL of pentane with stirring at 20 °C. While stirring is
continued, brick red crystals are formed, which are removed
by centrifugation after 15 h at 20 °C. (E,E)-14a is obtained
(Rf ) 0.5, 3:1 pentane/dichloromethane, total yield 480 mg,

[2-(Alkenyloxy)ethenyl]carbene Complexes
Organometallics, Vol. 15, No. 22, 1996 4851
1,3-phenylene), 77.0 (OCH2), 14.6 (CH3). IR (hexane) (cm-1
(%): ν ) 2057.1 (30), 1946.6 (100) [ν(CtO)]; 1561.0 (20) [ν-
(CdC)]. Anal. Calcd for C38H26Cr2O14 (810.6): C, 56.31; H,
3.23. Found: C, 56.45; H, 3.42.
89%). 1H NMR (C6D6): δ 7.28 and 7.05 (4:6 H, m each, 2 4-Ph),
7.03 (2 H, s, 2 3-H), 6.81 (4 H, s, 1,4-phenylene), 4.23 (4 H, q,
OCH2), 0.55 (6 H, t, CH3). 13C NMR (CDCl3): δ 302.3 (WdC),
204.0 and 197.9 [1:4, trans- and cis-CO, W(CO)5], 159.5 (Cq,
i-C, 1,4-phenylene), 151.7 (C4), 135.5 (Cq, i-C, 4-Ph), 131.5
(CH, C3); 130.4, 129.4, and 128.1 (2:2:1, CH each, 4-Ph), 118.2
(CH, 1,4-phenylene), 78.8 (OCH2), 14.1 (CH3). IR (hexane)
(cm-1) (%): ν ) 2064.6 (30), 1982.6 (5), 1942.0 (100) [ν(CtO)];
1553.5 (20) [ν(CdC)]. Anal. Calcd for C38H26O14W2 (1074.3):
C, 42.48; H, 2.44. Found: C, 42.42; H, 2.57.
µ-(1,4-P h en ylen e)bis[(2-eth oxy-4-p h en yl-1,1,1,1,1-p en -
ta ca r bon yl-1-ch r om a -1,3-bu ta d ien -4-yl)oxy] [(E,E)-14b].
Pentacarbonyl(1-ethoxy-3-phenyl-2-propynylidene)chromium
(1b) (385 mg, 1.00 mmol) and 1,4-dihydroxybenzene (13) (55
mg, 0.50 mmol) in 2.5 mL of diethyl ether is reacted as
described above to give (E,E)-14b (Rf ) 0.5, 3:1 pentane/
dichloromethane, total yield 308 mg, 76%). 1H NMR (C6D6):
δ 7.30 and 6.95 (4:6 H, m each, 2 4-Ph), 7.02 (2 H, s, 2 3-H),
6.80 (4 H, s, 1,4-phenylene), 4.32 (4 H, q, OCH2), 0.55 (6 H, t,
CH3). 13C NMR (CDCl3): δ 328.3 (CrdC), 224.0 and 216.7 [1:4,
trans- and cis-CO, Cr(CO)5], 158.5 (Cq, i-C, 1,4-phenylene),
151.5 (C4), 134.9 (Cq, i-C, 4-Ph), 129.9 (CH, C3); 129.0, 128.9,
and 128.0 (2:2:1, CH each, 4-Ph), 122.6 (CH, 1,4-phenylene),
75.8 (OCH2), 13.9 (CH3). IR (hexane) (cm-1) (%): ν ) 2058.5
(30), 1938.1 (100) [ν(CtO)]; 1554.3 (20) [ν(CdC)]. Anal. Calcd
for C38H26Cr2O14 (810.6): C, 56.31; H, 3.23. Found: C, 56.42;
H, 3.56.
µ-(1,3-P h en ylen e)bis[(2-eth oxy-4-p h en yl-1,1,1,1,1-p en -
t a ca r b on yl-1-ch r om a -1,3-b u t a d ien -4-yl)oxy] [(E,E)-16b
a n d (Z,Z)-16b ]. Pentacarbonyl(1-ethoxy-3-phenyl-2-propy-
nylidene)chromium (1b) (385 mg, 1.00 mmol) and 1,3-dihy-
droxybenzene (15) (55 mg, 0.50 mmol) in 2.5 mL of diethyl
ether is reacted as described above to give an 8:1 mixture of
16b (1H NMR analysis at 10 °C), from which (E,E)-16b is
isolated by fractionating crystallization at -15 °C as brick-
red crystals. Workup by (rapid) chromatography on silica gel
(20 × 2 cm column) with pentane/dichloromethane (5:1 to 3:1)
affords a red fraction of an isomer mixture of 16b (Rf ) 0.5,
4:1 pentane/dichloromethane, total yield 365 mg, 90%). After
16 h at 20 °C the isomer ratio has changed to (E,E/Z,Z)-16b
) 1:5. Crystallization at -15 °C affords (Z,Z)-16b (black
crystals, mp 116 °C).
)
P en ta ca r bon yl[1-(cycloh exyla m in o)-2-oxo-4-p h en yl-4-
p h en oxybu ten ylid en e]ch r om iu m (18) a n d 2-Eth oxy-N-
cycloh exyl-1-oxo-4-p h en oxy-4-p h en yl-3-bu ten a m id e (19).
To 2-ethoxy-4-phenyl-4-phenoxy-1,1,1,1,1-pentacarbonyl-1-
chroma-1,3-butadiene (10b) (444 mg, 1.00 mmol) and water
(18 mg, 1.00 mmol) in 1 mL of diethyl ether in a 5-mL airtight
screw-top vessel is added cyclohexyl isocyanide (109 mg, 1.00
mmol) in 3 mL of diethyl ether dropwise with stirring at 0 °C.
According to TLC starting material is consumed completely
after a few minutes. Workup by chromatography on silica gel
(20 × 2 cm column) with pentane/dichloromethane (1:1) affords
an orange fraction of 18 (Rf ) 0.5 in dichloromethane, 315 mg,
60%, orange crystals from dichloromethane/pentane (1:3) at
-15 °C) and a colorless fraction with 19 (Rf ) 0.2 in dichlo-
romethane, 91 mg, 24%, colorless oil).
18. 1H NMR (C6D6): δ 9.23 (1 H, s broad, NH); 7.23, 6.95
and 6.55 (2:2:1 H, m each, 4-Ph), 6.80 (5 H, m, 4-phenoxy),
7.02 (1 H, s, 3-H), 4.05 (1 H, m, NCH); 1.72, 1.63, 1.55, and
1.00 (2:2:1:5 H, m each, Cy). 13C NMR (C6D6): δ 265.8 (CrdC),
223.0 and 216.9 [1:4, trans- and cis-CO, Cr(CO)5], 194.0 (Cq,
CdO), 163.4 (Cq, i-C, phenoxy), 155.4 (C4), 133.1 (Cq, i-C,
4-Ph), 130.9 (CH, C3); 129.7, 128.7, and 128.0 (2:2:1, CH each,
4-Ph); 123.9, 118.5, and 112.4 (2:1:2, CH each, phenoxy); 62.6
(NCH); 31.9, 24.7, and 24.1 (2:1:2, CH2 each). IR (diffuse
reflection) (cm-1) (%): ν ) 2055.2 (30), 1977.2 (10), 1950.4 (100)
[ν(CtO)]; 1587.2 (20) [ν(CdC)]. MS (70 eV) [m/e (%)]: 525
(5) [M+], 497 (10), 441 (30), 413 (20), 385 (50) (60) [M+ - 5CO],
94 (100). Anal. Calcd for C27H23CrNO7 (525.5): C, 61.71; H,
4.41; N, 2.67. Found: C, 61.83; H, 4.62; N, 2.80.
19. 1H NMR (C6D6): δ 7.50, 7.05, and 6.70 (2:2:1 H, m each,
4-Ph); 7.25 and 6.95 (2:3 H, m, 4-phenoxy), 6.85 (1 H, d broad,
NH), 5.90 and 4.95 (1 H each, AB system, 3J ) 9.5 Hz, 2-H
and 3-H), 3.90 (1 H, m, NCH), 3.50 and 3.20 (1 H each,
diastereotopic OCH2); 2.05, 1.80, 1.45, 1.30, 1.23 (1:2:2:2:3 H,
m each, Cy), 1.03 (3 H, t, CH3). IR (diffuse reflection) (cm-1
)
(%): ν ) 3430 (20) [ν(N-H)], 1677.9 and 1519.5 [δ(N-H)],
1593.1 [ν(CdC)].
(E,E)-16b. 1H NMR (C6D6): δ 7.30 and 6.98 (4:6 H, m each,
2 4-Ph), 7.08 (2 H, s, 2 3-H); 6.90, 6.83, and 6.70 (1:1:2 H; t,
“s”, “d”; 1,3-phenylene), 4.35 (4 H, q, OCH2), 0.52 (6 H, t, CH3).
IR (hexane) (cm-1) (%): ν ) 2058.5 (30), 1938.1 (100) [ν(CtO)];
1554.3 (20) [ν(CdC)]. Anal. Calcd for C38H26Cr2O14 (810.6):
C, 56.31; H, 3.23. Found: C, 56.35; H, 3.43.
Ack n ow led gm en t. This work was supported by the
Volkswagen-Stiftung and the Fonds der Chemischen
Industrie. The authors thank Beate J asper and Bar-
bara Hildmann for skillful technical assistance.
(Z,Z)-16b. 1H NMR (C6D6): δ 7.52 (2 H, s, 2 3-H), 7.40 and
6.90 (4:6 H, m each, 2 4-Ph); 6.68, 6.46, and 6.40 (1:1:2 H; t,
dd, dd; 1,3-phenylene), 4.48 (4 H, q, OCH2), 0.80 (6 H, t, CH3).
13C NMR (CDCl3): δ 332.4 (CrdC), 224.2 and 217.0 [1:4, trans-
and cis-CO, Cr(CO)5], 158.4 (Cq, i-C, 1,3-phenylene), 143.1
(C4), 133.8 (Cq, i-C, 4-Ph), 130.7 (CH, C3); 129.5, 128.7, and
128.3 (2:1:2, CH each, 4-Ph), 111.2 and 105.5 (2:1 C, CH each,
Su p p or tin g In for m a tion Ava ila ble: Tables of data col-
lection parameters, positional and displacement parameters,
and bond distances and angles and SCHAKAL diagrams (37
pages). Ordering information is given on any current mast-
head page.
OM9604132