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An Organometallic Analogue of the УCriss-CrossФ Cycloaddition Reaction.

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(21 R. P. Ziebdrth, J. D. Corbett, 1 Am. Chem. Soc. 1985, 107, 4571.
(31 T. Hughbanks, G. Rosenthal, J. D. Corbett, J. Am. Chem. Soc. 1988, 110,
[4] E A. Cotton, P. A. Kibala, W. J. Roth, J. Am. Chem. Soc. 1988, 110, 298.
IS] We have also found that under slightly less reducing conditions square
pyramidal pentanuclear clusters of the composition [Zr,X,,(PR,),] are
formed. These will be described in detail at a later date.
(61 Further details of the crystal structure investigations are available on request from the Fachinformationszentrum Karlsruhe, Gesellschaft fur wissenschaftlich-technische Information mbH, D-W-7514 Eggenstein-Leopoldshafen 2 (FRG), on quoting the depository number CSD-56200, the
names of the authors, and the journal citation.
[7] R. P. Ziebarth, J. D. Corbett, 1 offsolid State Chem. 1989, 80, 56.
(81 F. A. Cotton, M. Shang, W. A. Wojtczak, Inorg. Chem. 1991, 30, 3670.
191 F. Rogel, J. D. Corbett, .
Am. Chem. Soc. 1990, 112, 8198.
[lo] J. D. Smith, J. D. Corbett. J. Am. Chem. Soc. 1985, 107, 5704.
[ l l l R. P. Ziebarth, J. D. Corbett, L Am. Chem. Soc. 1988, Iff, 3272.
sufficiently acidic to deprotonate spontaneously upon dissolution in CH,Cl, or THE Vinylidene complexes analogous
to 2a, b with organic substituents on the @-carbon are
known,15] but the unsubstituted derivatives 2a, b have not
been previously described. However, 2a has been proposed
as a reaction intermediate.I6]The complexes 2a, b have been
spectroscopically characterized, but they cannot be isolated
since upon warming to 22 “C they rapidly decompose, with
formation of the p-vinylidene complexes [(Cp(CO),M) &C=CH,)] .I6* ’I Consequently, they must be generated and
studied at low temperature.
The criss-cross cycloaddition product 3b was formed upon
addition of benzalazine to the vinylidene complex 2b [Eq.
@)I. IR monitoring indicates a clean transformation without
An Organometallic Analogue of the
“Criss-Cross” Cycloaddition Reaction **
By Colleen Kelley, Lisa A . Mercando, Michael R . Terry,
Noel Lugan, Gregory L. Geoffrey,* Zhengrian Xu,
and Arnold L. Rheingold
Azines have been known since 1917[’] to undergo consecutive [3 + 21 cycloaddition reactions with 1,3-dipolarophiles
to give bicyclic products having fused five-membered rings
[Eq. (a)], a transformation that is commonly known as the
criss-cross reaction.[’] Electron-rich azines typically require
3 b (53%)
detectable by-products, and 3b was isolated as a solid and
was spectroscopically characterized. A similar reaction occurs between the carbyne complex la and two equivalents of
benzalazine to give the analogous product 3a, with the second benzalazine equivalent necessary to deprotonate the intermediate formed between l a and the azine. The ORTEP
drawing of 3a {see Fig. 1 l8I) shows the fused five-membered
rings to be nearly planar [max. deviation = 0.17 A at C(20)]
as is the entire bridging ligand (dihedral angle [C(15)-N(I)N(2)-C(17)]-[C(20)-N(l)-N(2)-C(l8)]
= 171.5’). The Mn-
electron-deficient alkenes as partners and often need elevated temperatures and prolonged reaction times. In contrast,
azines with electron-withdrawing CF, substituents react
with a variety of substrates, including electron-rich
oIefins.“, 31 We report herein the first examples of
organometaltic analogues of this criss-cross cycloaddition
involving benzalazine and vinylidene or carbyne complexes.
I t has been found that the ethylidyne complexes 1 undergo
deprotonation to form the new vinylidene complexes 2.
This deprotonation may be accomplished by treating complexes 1 with Et,N, although the rhenium complex l b is
[*] Prof. G. L. Geoffroy, Dr. C. Kelley, L. A. Mercando, M. R. Terry
Department of Chemistry, The Pennsylvanla State University,
University Park, PA 16802 (USA)
Dr. N. Lugan
LdbOrdtOire de Chimie de Coordination du CNRS, Toulouse (France)
2. Xu, Prof. A. L. Rheingold
Department of Chemistry, University of Delaware, Newark, DE (USA)
This work was supported by the OKice of Basic Energy Sciences, U.S.
Department of Energy, and a NATO Cooperative Research Grant.
Anget<’.Chem. Int. Ed. Engl. 1992, 31, No. X
Fig. I . An ORTEP drawing of 3a. Selected bond lengths [A]; Mn(1)-CP(l),
1.791(4); Mn(2)-Cp(2), 1.782(4), Mn(I)-C(15), 1.945(3); Mn(2)-C(18),
1.936(3); N(l)-N(2), I .438(3); N(l)-C(20), 1.472(4); N(l)-C(l S), 1.312(4);
N(2)-C(17), 1.473(4); N(2)-C(lS), 1.306(4).
C(carbene) bond lengths of 1.945(3) and 1.936(3) A lie in
the typical range.[’’ The planes defined by the carbene carbon atoms and their attached carbon and nitrogen substituents do not bisect the CO-Mn-CO angle, as often found
for [Cp(CO),Mn=CRR‘] carbene cornple~es,~’~
but instead
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appear to be oriented so as to minimize steric interactions.
The two benzylic carbons of the bridging organic ligand are
both chiral, and thus the molecule could be present as a pair
of enantiomers or in the meso form. However, NMR data
indicates only the formation of a single spectroscopically
detectable stereoisomer, and the crystal structure shows it to
be the RRjSS pair with the two phenyl groups on the same
side of the fused five-membered rings.
The reaction mechanism proposed for the formation of
3b resembles that which has been established for organic
analogues of this criss-cross reactioni2](Scheme 1). The a-
a chromium analogue of 7 could be isolated, a vinylidene
complex was proposed as intermediate.['31
The above reactions demonstrate that the vinylidene complex 2b is a highly reactive species, and in particular the
criss-cross cycloaddition with benzalazine indicates that this
complex is a potent 1,3-dipolarophile which should be capable of undergoing cycloadditions with a variety of other substrates. Interestingly, the manganese vinylidene complex 2a does not readily react with benzalazine and
tBuN=C=NtBu, implying a decreased electrophilicity of the
vinylidene a-carbon in 2a compared to that in the rhenium
complex 2b. However, the much more electrophilic carbyne
complex l a does react rapidly with each of these substrates
to give, after treatment with Et,N, the analogous complexes
3a, 5a, and 6a. Thus, in the manganese reactions deprotonation must be accomplished after substrate addition, but in
the rhenium case it occurs before addition.
Scheme 1. Proposed mechanism for the formation of 3b; [MI = Cp(CO),Re.
carbon of vinylidene complexes is known to be electrophili~,[~]
and the cycloaddition reaction is most likely initiated by addition of the azine nitrogen to this carbon in 2b.
Cyclization then ensues to give 4, an organic analogue of
which is known.t3"1 Addition of the nucleophilic nitrogen of
4 to a second equivalent of 2b with subsequent cyclization
would give 3b. The carbyne complex l a is believed to react
in a similar fashion but with deprotonation of the methyl
substituent occurring after the initial addition of the azine
nitrogen to the carbyne carbon.''']
Vinylidene complex 2b also undergoes [2 + 21 cycloaddition with PhN=CHPh to give the carbene complex 5b [Eq.
(c)], a reaction which has precedent in the cycloaddition of
5b (49%)
imines with vinylidene iron complexes.[' A novel transformation of vinylidene complexes is that with 2b and
tBuN=C=NtBu to form the isocyanide complex 6b [Eq.
(d)].['2J This reaction represents a net metathesis of the
vinylidene C=C bond with the N=C bond of the carbodiimide and may proceed via the intermediate carbene
complex 7, which could undergo a retro-cycloaddition to
give the observed products. For the addition of
C6Hl,N=C=NC,H,, to [(CO),Cr=C(OH)CH,], in which
Received: January 24,1992 [Z 5146 IE]
German version: Angew. Chem., 1992, 104, 1066
CAS Registry numbers:
l a , 81616-28-6; 1b, 141902-81-0; 2a, 141902-82-1; 2b, 141902-83-2; 4a,
141902-84-3: 4b, 141902-85-4: Sa, 83111-32-4; Sb, 141902-86-5; [Cp(CO),Mn=CCHJBCl,, 59831-16-2: [Cp(CO),Re=CCH,]BCI,, 141902-80-9;
PhCH=NCH,, 622-29-7; tBuN=C=NBut, 691-24-7: benzalazine, 588-68-1.
Dissolution of [Cp(CO),Re=CCH,][BCl,l in CH,CI, at - 50 "C gave immediate deprotonation to yield gaseous HCI (the vapors turned litmus paper red)
and complex 2b, (detected by IR). A two-fold excess of benzalazine was added,
the mixture was stirred for 1 h at 0 "C, the solvent was removed under vacuum,
and the residue was chromatographed on neutral alumina to afford a yellow
band of PhCH=NN=CHPh [eluent: CH,Cl,/hexane (1 :I)] as well as a yellow
band of 3b [eluent: CH,Cl,jhexane (3: 1); 53 % yield]. To prepare 3a, a two-fold
excess of benzalazine was added to a -50°C THF solution of [Cp(CO),MnsCCH,]BCI,, and the solution was stirred at - 50 "C for 3 h followed
by warming to 22 "C and evaporation of solvent under vacuum to afford a red
oil which was chromatographed on neutral alumina to give first a yellow band
of PhCH=N-N=CHPh [eluent: CH,Cl,/pentane (1 :I)] followed by a yellow
band of 3a (eluent: 100% CH,CI,; 41 %yield). 2a: IR (CH,CI,, ca. -SOT):
5[cm-']=1998, 1935 (CO), 1623 (C=C); Zb: IR (CH,CI,, ca. -50°C:
a [cm-']= 1990, 1915 (CO), 1629 (C=C); 'H NMR (300 MHz, CD,CI,,
- 1 O T) : 6 = 2.32 (s, 2H, CH,), 5.48 (s, 5H, Cp). 3a: 'H NMR (300MHz,
C6D6,25°C): 6 =7.38-6.99 (Ph), 5.34 (dd, J=10.2, 2.4Hz, CHPh), 4.03 (s,
Cp),3.34(dd, I H , J=18.4. 10.2Hz,CHZ),3.10(dd, J=18.4,2.4Hz,CH2).
"CC('H) NMR (75.5 MHz, CD,CI,, 25°C): 6 = 245.5 (Mn = C), 233.95,
232.89 (CO), 140.6-126.8 (Ph), 84.0 (Cp), 66.25 (CHPh), 59.26 (CH,). IR
(CH,CI,): C [cm-']=1926, 1858 (CO). MS (FAB): mjz = 612 (M@).
'HNMR (300 MHz, C,D,, 25°C): 6 =7.8-6.7 (Ph), 4.91 (s, SH, Cp), 4.03 (dd,
J =7 . 5 , 2.4Hz. CHPh), 1.85 (dd, l H , J=16.6, 7.5Hz, CH,), 1.81 (dd, l H ,
J =16.6, 2.4 Hz, CH,). 13C{1H)NMR (75.5 MHz, CD,CI,, 25°C): 6 = 228.3
(Re = C), 206.9, 206.5 (CO), 148.2-125.9 (Ph), 87.5 (Cp), 38.3 (CHPh), 22.6
(CH,). IR (CH,CI,): 5 [cm-'1 = 1926, 1847 (CO).
(Q VCH Verlagsgesellschafi mbH, W-6940 Weinheim, 1992
J. R. Bailey, N. H. Moore, J. Am. Chem. SOC.1917, 39*279; J. R. Bailey,
A. T. McPherson, ibid. 1917, 40, 1322.
A. Padwa, 1.3-Dipolar Cycloaddirion Chemisfry, Wiley, New York, 1984;
T. Wagner-Jauregg, Synthesis 1976, 349.
A. G. Gieren, P. Narayanan, K. Burger, W. Thenn, Angew. Chem. 1974,
86,482; Angew. Chem. Inr. Ed. Engl. 1974,13,475; 0. Nuyken, G. Maier,
K. Burger, Makromol. Chem. 1988, 189, 2245; ibid. 1989, 190, 623; K.
Burger, F. Hein, Justus Liebigs Ann. Chem. 1982, 853; K. Burger, H.
Schickaneder, F. Hein, A. Gieren, V. Lamm, H. Engelhard, ibid. 1982,845;
K. Burger, W. Thenn, R. Rauh, H. Schickaneder, A. Gieren, Chem. Ber.
1975, 108, 1460.
E. 0. Fischer, G. Z. Besl, Z . Naturforsch. B 1979,34, 1186; E. 0. Fischer,
R. L. Clough, P. Stiickler, J. Organomer. Chem. 1976, 120, C6.
a) M. I. Bruse, Chem. Rev. 1991, 91, 197; b) M. I. Bruce, A. G. Swincer,
Adv. Organomet. Chem. 1983,22, 59.
K.Folting, J. C. Huffman, L. N. Lewis, K. G. Caulton, Inorg. Chem. 1979,
18, 3483; B. E. Boland-Lussier, M. R. Churchill, R. P. Hughes, A. L.
Rheingold, Organomeiallics 1982, 1, 628.
The new compound [Cp(CO),Rel,(p-C=CH,)
[IR (CH,CI,):
5 [cm-'1 = 1977(w), 1948(s), 1900(s) (CO)] is similar to [{Cp(CO),Re},(pC=CHPh)]: N. E. Kolobova, A. B. Antonova, 0. M. Khitrova, M. Y Antipin, Y. T. Struchkov, J. Organornet. Chem. 1977, 137, 69.
OS70-0833/92/0808-1054$3.50+ ,2510
Angew. Chem. Int. Ed. Engl. 1992, 31, No. 8
[8] C,,H,,Mn,N,O,:
triclinic, P1, a =10.652(5), b =10.870(3), c =
13.199(6) A, a =75.97(3), fl = 67.85(3), y = 82.54(3)", V =1372.0(9) A',
Z = 4. R(F) = 0.0391, T = 297 K. . Further details of the crystal structure
investigation are available upon request from the Director of the Cambridge Crystallographic Data Centre, University Chemical Laboratory,
Lensfield Road, GB-Cambridge CB21EW (UK), on quoting the full journal citation.
[9] K. H. Dotz, H. Fischer, P. Hoffmann, F. R. Kreissl, U. Schubert, K.
Weiss, Transition Metal Carbene Complexes, Verlag Chemie, Weinheim,
[lo] For related reactions of l a see: 9. Handwerker, K. E. Garrett, K. L. Nagle, G. L. Geoffroy, A. L. Rheingold, Orgunometallics 1990, 9, 1562; H.
Fischer, C. Troll, J. Organornet. Chem. 1992, 427, 17.
[ll] A. G. M. Barrett, J. Mortier, M. Sabat, M. A. Sturgess, Organometallics
1988, 7, 2553; A. G. M. Barrett, M. A. Sturgess, J. Org. Cltem. 1987, 52,
3940; Telruhedron Left. 1986, 27, 381 1.
[12] G. W. Harris, J. C. A. Boeyens, N. J. Coville, J. Organomet. Chem. 1983,
255, 87.
[I31 K. Weiss, E. 0. Fischer, J. Miiller, Chem. Ber. 1974, 107, 3548.
dimer was used successfully as a building block for cyclic
phosphorusxarbon compounds,[71cleavage reactions of the
metal complex fragments of the other complexes have so far
been unsuccessful.
Herein we report for the first time a spirocyclotrimerization of the phosphaalkyne 5[*]in the presence of aluminum
trichloride. In dichloromethane this reaction occurs highly
selectively ( 295 %) in a 3 : 1 molar ratio and gives betaine 8
with the incorporation of the Lewis acid. First indications of
a cyclooligomerization were provided by the 'H NMR spectrum, which showed three different tert-butyl groups
(Table I), and the 31P NMR spectrum, in which the three
observed absorptions lie at completely different S values
Spirocyclization of a Stable Phosphaalkyne
with Aluminum Trichloride-Key Reaction
for the Production of Triphospha Dewar Benzene
By Bernhard Breit, Uwe Bergstrasser, Gerhard Maas,
and Manfred Regitz*
MIO"' C o
c\ co
[*] Prof. Dr. M. Regitz, DipLChem. B. Breit, Dipl.-Chem. U. Bergstrasser,
Prof. Dr. G. Maas
Fachbereich Chemie der Universitlt
D-W-6750 Kaiserslautern (FRG)
[**I Phosphorus Compounds, Part 58. This work was supported by the Volkswagen-Stiftung and the Fonds der Chemischen Industrie. Part 57: M.
Birkel. J. Schulz, U. Bergstrasser, M. Regitz, Angew. Chem. 1992,104,870;
Angew. Chem. Int. Ed. Engl. 1992,31,879.
Angew. Chem. Int. Ed. Engl. 1992, 31, No. H
The organometallic chemistry of phosphaalkynes received
considerable impetus from cyclooligomerization reactions,
in which their metal complex fragments were incorporated
into the products.''] Significant milestones along this route
include the cyclodimerization of tert-butylphosphaacetylene
5 to give the 1,3-diphosphacyclobutadienecomplexes 1 (e.g.,
with cyclopentadienylrhodium[21or -cobalt fragmentsL3I),
the unusual linkage of 5 to the tricyclic zirconium complex
2,["l and finally the cyclotrimerization of 5 to give the molybdenum compound 3 of 1,3,5-triphosphaben~ene,[~I
as well as
the Dewar isomer 4 with vanadium as the central metal
atom.[61Whereas in the case of 2 the true phosphaalkyne
Dedicated to Professor Giinter Maier
on the occasion of his 60th birthday
[Table 1; 6 = - 80.1 (P3), 261.4 (Pl), 417.9 (P5)]. The two
latter absorptions indicate that the reaction product still has
Table 1. Selected physical data for the spirocyclic betaine 8 as well as for the
tetracycles 12 and 13 [a].
8; 'H N MR : 6 =1.34 (dd, 4J(P,H) = 0.7, 0.8Hz, 9 H , tBu), 1.43 (d, 4J(P,H)
=1.2Hz, 9 H , IBu), 1.59 (pseudo-t, 4J(P,H) = 0.9 Hz, 9 H , rBu); ' T N M R :
6 = 31.9 (s, C(CH,),), 33.8 (pseudo-t, ,J(P,C) = 9.2 Hz, C(CH,),). 34.9 (dd,
'J(P,C) = 1 2 . 2 H ~ , "J(P,C) =12.5, 4.5 Hz, C(CH,),), 41.1 (d, 'J(P,C) =
8.4 Hz, C(CH,),), 43.6 (pseudo-t, 'J(P,C) = 2.0 Hz, C(CH,),), 48.1 (d, ,J(P,C)
= 3.0 Hz, C(CH,),), 202.9 (d, 'J(P,C) = 65.4 Hz, P = C), 245.9 (dd, 'J(P.C)
= 68.2, 81.7 Hz, P = C); ,'PNMR: 6 = - 80.1 (d, 'J(P,P) = 214.5 Hz, P3),
261.4 (dd, 'J(P,P) = 214.5 Hz, 'J(P,P) =18.0 Hz, Pl), 417.9 (d, 'J(P,P) =
18.0 Hz, P5).
12; 'H N MR : d = 0.96 (s, 9H, tBu), 1.40 (d, 4J(P,H) = 0.9 Hz, 9 H , tBu), 1.43
(d, 4J(P,H) 1.5 Hz, 9 H , tBu), 1.58 (pseudo-t, +J(P,H) =1.4Hz, 9H, rBu);
' T N M R : 6 = 31.9 (dd, 'J(P,C) =15.1 Hz, 4J(P,C) = 6.0 Hz, C(CH,),), 32.6
(pseudo-t, ,J(P<C) =10.1 Hz, C(CH,),), 33.1 (pseudo-t, 'J(P,C) = 14.6 Hz,
C(CH,),), 34.7 (s, C(CH,),), 36.7 (d, *J(P,C) =12.1 Hz, C(CH,),), 36.9, 38.2,
40.8 (each m, each C(CH,),), 42.1,58.2 (each m, C2/C3), 96.7 (m. CS), 21 1.6 (m,
'28); "P NMR: 6 = - 160.0 (pseudo-quintet, 'J(P,P) = 32.9, 16.6 Hz,
,J(P.P) =13.2 Hz, P4), 111.5 (d, pseudo-t, *J(P.P) = 33.1, 32.9, 16.6 Hz, PI),
134.3 (ddd, 'J(P,P) = 264.8 Hz, ,J(P,P) = 33.1,19.8 Hz,P6),417.1 (d, pseudot, 'J(P,P) = 264.8 Hz, 'J(P,P) =13.2 Hz, P7); MS(70 eV): mjz 401 (M" + H,
20%), 355 ( M Q - 3 Me, 5), 300 ( M e - tBuCP, 10). 262 (M" - 2 tBuC, 25),
200 (M" - 2 CBUCP,8), 169 ( M e - 2 IBuCP, -P, 100).
13: 'H N MR : 6 =1.00,1.17,(eachs,each9H,tBu),1.43(d.4J(P,H) =2.0Hz,
9H, ~Bu),1.80 (S, 9H, ~ B u ) ;"CNMR: 6 = 29.9 (d, ,J(P,C) = 8.4Hz,
C(CH,),), 31.3 (s, C(CH,),), 31.6 (d. ,J(P,C) =11.4 Hz, C(CH,),), 33.9 (d,
'J(P,C) = 6.1 Hz, C(CH,),), 36.5 (pseudo-t, ,J(P,C) = 20.6 Hz, C(CH,),),
37.0 (d, '4P.C) = 9.2 Hz, C(CH,),), 39.1 (pseudo-t, 'J(P,C) = 12.2 Hz,
C(CH,),), 41.0 (pseudo-t, ,J(P,C) = 16.0 Hz, C(CH,),), 60.1 (pseudo-t,
'J(P,C) = 34.3 Hz, C2), 64.2, 89.3 (each m, CS/C6), 224.3 (pseudo-t,
'J(P,C) = 54.2 Hz, C8); 31PNMR: 6 = - 174.4 (d, 'J(P,P) = 83.0 Hz. P3 or
P4), - 147.3 (ddd, 'J(P,P) = 83.0 Hz, 'J(P,P) = 31.2, 16.6 Hz, P3 or P4), 64.6
(d, 'J(P,P) = 31.2 Hz, PI), 399.0 (s, P7); MS(70 eV): m/z401 (M" + H, 45%),
300 ( M e - tBuCP, lo), 262 (M" - 2 tBuC, 62). 200 ( M Q- 2 tBuCP, 221,169
( M e - 2 IBuCP, -P, 100).
[a] 'H (90 or400 MHz, TMS), 13C(100.6 MHz, TMS), and "P NMR spectra
(80.8 MHz, 85% H,PO,) in CD,Cl, for 8, in C,D, for 12, 13.
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organometallic, уcriss, reaction, cycloadditions, cross, analogues
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