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The ability of several tungsten carbene complexes to initiate alkyne polymerization has been known for long time : T. J. Katz, S. J. Lee, J. Am. Chem. Soc. 1980, 102, 422-424.
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The incorporation of three units of a terminal aromatic alkyne to a 3-dimethylamino-3-trimethylsilylpropylidenchromium(0) complex has been reported: a) F. Stein, M. Duetsch, R. Lackmann, M. Noltemeyer, A. de Meijere, Angew. Chem. 1991, 103, 1669-1671;
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Compound 4a: C32H38CrO5; M τ, 554.6; crystal size, 0.50 × 0.45 × 0.27 mm 3; monoclinic; P21/n; a, 9.0928(4, b, 18.2604(8, c, 16.9883(8) Å α, 90.000(1, β, 95.635(1, γ, 90.000(1)°; V, 2807.08(4) Å3; Z, 4; ρ= 1.312 Mgm-3; μ, 0.447 mm-1; λ, 0.71073 Å; T= 100(2) K; 2θ;mat, 56.6; reflections collected/unique 17757/6623; R(int, 0.025, final R indices [I > 2σ(I, R1, 0.039, wR 2, 0.095, R indices (all data) R1, 0.066, wR2, 0.108, Compound 9, isomer B: C47H38CrO4; Mr, 718.81; crystal size, 0.22 × 0.15 × 0.07 mm 3; triclinic; P1̄, a, 11.4230(17, b, 12.681(2, c, 13.9518(15) Å; α, 78.434(12, β, 79.714(11, γ, 72.161(14)°; V= 1869.8(5) Å
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2 = 0.116; CCDC-616298 (4a), -616299 (4f isomer B) and -648 137 (9 isomer B) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.cccdc.cam.ac.uk/data_request/cif.
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Pentacarbonyl alkyne-carbene complexes and more rigid tetracarbonyl alkyne-chelated ones have also been isolated and proposed as intermediates in a bimetal-assisted intermolecular insertion, leading finally to dimerization and forming centrosymmetric chrysenes: F. Hohmann, S. Siemoneit, M. Nieger, S. Kotila, K. H. Dötz, Chem. Eur. J. 1997, 3, 853-859
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Pentacarbonyl alkyne-carbene complexes and more rigid tetracarbonyl alkyne-chelated ones have also been isolated and proposed as intermediates in a bimetal-assisted intermolecular insertion, leading finally to dimerization and forming centrosymmetric chrysenes: F. Hohmann, S. Siemoneit, M. Nieger, S. Kotila, K. H. Dötz, Chem. Eur. J. 1997, 3, 853-859.
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for examples of 1,2- and 1,3-chromium migrations in FCC chemistry, respectively, see: b) J. Barluenga, M. Tomás, E. Rubio, J. A. López-Pelegrín, S. García-Granda, P. Pertierra, J. Am. Chem. Soc. 1996, 118, 695-696;
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For an example of the more common exo-regioselective intramolecular insertion of an alkyne in an anionic oxycarbene complex see: H. Rudler, A. Parlier, V. Certal, J. Vaissermann, Angew. Chem. 2000, 112, 3559-3561;
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For an example of the more common exo-regioselective intramolecular insertion of an alkyne in an anionic oxycarbene complex see: H. Rudler, A. Parlier, V. Certal, J. Vaissermann, Angew. Chem. 2000, 112, 3559-3561;
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The insertions of carbonyl ligands in carbonyl metallate complexes have been previously described for different metals: Ni: a) E. J. Corey, L. S. Hegedus, J. Am. Chem. Soc. 1969, 91, 4926-4928; Fe:
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As suggested by one of the reviewers, the transformation of XI into XIV could also proceed via a vinylidene complex and subsequent alkenyl-vinylidene coupling. This also could explain the different product types in the reaction of 3 a with internal and terminal alkynes. However, we are not aware of such behaviour for chromium, although it is well documented for other metals, such as osmium: D. Huang, M. Oliván, J. C. Huffman, O. Eisenstein, K. G. Caulton Organometallics 1998, 17, 4700-4706.
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As suggested by one of the reviewers, the transformation of XI into XIV could also proceed via a vinylidene complex and subsequent alkenyl-vinylidene coupling. This also could explain the different product types in the reaction of 3 a with internal and terminal alkynes. However, we are not aware of such behaviour for chromium, although it is well documented for other metals, such as osmium: D. Huang, M. Oliván, J. C. Huffman, O. Eisenstein, K. G. Caulton Organometallics 1998, 17, 4700-4706.
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