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Other methods
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The first reported carbene transmetalation involved a molybdenum methoxycarbene to form an iron and, presumably, a Ni carbene Fischer, E. O.; Beck, H.-J. Angew. Chem., Int. Ed. Engl. 1970, 9, 72-73.
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A ligand-stabilized Pd alkoxycarbene has been recently isolated using transmetalation: López-Alberca, M. P.; Mancheño, M. J.; Fernández, I.; Gómez-Gallego, M.; Sierra, M. A.; Torres, R. Org. Lett. 2007, 9, 1757-1759.
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40
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51249119653
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The different rates of carbene rotation in the monomelic and the dimeric complexes could be due to the different geometrical constraints in both complexes. However, it looks more likely that the rotation of the carbene in the dimers requires cleavage of at least one of the chloro bridges
-
The different rates of carbene rotation in the monomelic and the dimeric complexes could be due to the different geometrical constraints in both complexes. However, it looks more likely that the rotation of the carbene in the dimers requires cleavage of at least one of the chloro bridges.
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41
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51249116919
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Complex 1 shows a fiuxional behavior in CD3CN solutions. A mixture of three species, but no free SMe2, was found when 1 was dissolved in CD3CN and cooled to 233 K. Thus, these species can be tentatively assigned to the three isomers of [PdClMe(SMe 2)NCCD3, Pd-Me, δ 0.68, 0.53, 0.36, These complexes undergo fast exchange upon warming to give, at 263 K, the average Pd-Me signal shown in Figure 2 and broad SMe2 resonances around 2.3 ppm. This is not observed for the acyl derivative 8, which at 233 K in CD3CN shows only one species with coordinated SMe2
-
2.
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42
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0000570812
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3): Hayashi, Y.; Isobe, K.; Nakamura, Y.; Okeya, S. J. Organomet. Chem. 1986, 310, 127-134.
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3): Hayashi, Y.; Isobe, K.; Nakamura, Y.; Okeya, S. J. Organomet. Chem. 1986, 310, 127-134.
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43
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51249093678
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Reaction mixtures were cooled to 233 K, at different times and conversions, to slow down the exchange process that affects 1, in order to facilitate the observation of a possible palladium methyl carbene complex. Cooling led to better resolved spectra, but no complex of this type was detected.
-
Reaction mixtures were cooled to 233 K, at different times and conversions, to slow down the exchange process that affects 1, in order to facilitate the observation of a possible palladium methyl carbene complex. Cooling led to better resolved spectra, but no complex of this type was detected.
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44
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51249098293
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We have checked the CO transfer ability of these types of tungsten complexes, W(CO)5(NCMe, reacts with 1 to give 8, demonstrating that not only 3 but also the reaction byproducts can be the source of CO in the carbonylation. In other words, the carbonylating agent is not necessarily consumed (although its nature changes) as the carbonylation proceeds, this helping to keep the carbonylation rate high
-
5(NCMe)] reacts with 1 to give 8, demonstrating that not only 3 but also the reaction byproducts can be the source of CO in the carbonylation. In other words, the carbonylating agent is not necessarily consumed (although its nature changes) as the carbonylation proceeds, this helping to keep the carbonylation rate high.
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Komiya, S.6
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46
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51249124671
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Wilkinson, G, Stone, F. G. A, Abel, E. W, Eds, Pergamon: Oxford, U.K, Chapter 26.1, p
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37049109848
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A synthetic procedure analogous to that for the complex [PdCl 2(tht)2] was used
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2] was used: Usón, R.; Forniés, J.; Martínez, F.; Tomás, M. J. Chem. Soc., Dalton Trans. 1980, 888-893.
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51249083708
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Data analysis and drawing were performed with the programs SMART V5.051 (1998), SAINT V6.02 (1999), and: Sheldrick, G. M. SHELXTL V5.1; Bruker AXS, Inc., Madison, WI, 1998.
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Data analysis and drawing were performed with the programs SMART V5.051 (1998), SAINT V6.02 (1999), and: Sheldrick, G. M. SHELXTL V5.1; Bruker AXS, Inc., Madison, WI, 1998.
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