Synthesis, structure, and reactivity of nitrosyl pincer-type rhodium complexes

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Pincer-type linear nitrosyl Rh(I) complexes, Rh(PCPBu)(NO)][BF4] (2) and [Rh(PCPBuCH2)(NO)][BF,4] (8), are reported (PCPBu = 1,3-bis[(di-fer/-butylphosphino)methyl]-2,4,6-trimethylbenzene). Complex 2 was synthesized by reaction of the Rh(I) dinitrogen complex Rh(PCPBu)N 2 (1) with NOBF2, while treat...

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Autor principal: Gaviglio, C.
Otros Autores: Ben-David, Y., Shimon, L.J.W, Doctorovich, F., Milstein, D.
Formato: Capítulo de libro
Lenguaje:Inglés
Publicado: 2009
Acceso en línea:Registro en Scopus
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Biblioteca Central Dr. Luis F. Leloir (FCEN) de Universidad de Buenos Aires
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030 |a ORGND 
100 1 |a Gaviglio, C. 
245 1 0 |a Synthesis, structure, and reactivity of nitrosyl pincer-type rhodium complexes 
260 |c 2009 
270 1 0 |m Milstein, D.; Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Spain; email: david.milstein@weizmann.ac.il 
506 |2 openaire  |e Política editorial 
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504 |a Morales-Morales, D., Lee, D.W., Wang, Z., Jensen, C.M., (2001) Organometallics, 20, p. 1144 
504 |a Haenel, M.W., Oevers, S., Angermund, K., Kaska, W.C., Fan, H.J., Hall, M.B., (2001) Angew. Chem, 113, p. 3708 
504 |a (2001) Angew. Chem., Int. Ed, 40, p. 3596 
504 |a Gottker- Schnetmann, I., White, P.S., Brookhart, M., (2004) J. Am. Chem. Soc, 126, p. 1804 
504 |a Hermann, D., Gandelman, M., Rozenberg, H., Shimon, L.J.W., Milstein, D., (2002) Organometallics, 21, pp. 812-818 
504 |a Ben-Ari, E., Gandelman, M., Rozenberg, H., Shimon, L.J.W., Milstein, D., (2003) J. Am. Chem. Soc, 125, pp. 4714-4715 
504 |a Ben-Ari, E., Gandelman, M., Shimon, L.J.W., Martin, J.M.L., Milstein, D., (2006) Organometallics, 25, pp. 3190-3210 
504 |a Feller, M., Karton, A., Leitus, G., Martin, J.M.L., Milstein, D., (2006) J. Am. Chem. Soc, 128, pp. 12400-12401 
504 |a Ben-Ari, E., Leitus, G., Schimon, L.J.W., Milstem, D., (2006) J. Am. Chem. Soc, 128, pp. 15390-15391 
504 |a Zhang, J., Gandelman, M., Shimon, L.J.W., Milstein, D., (2004) Oreanometallics, 23, pp. 4026-4033 
504 |a Zhang, J., Leitus, G., Ben-David, Y., Milstein, D., (2005) J. Am. Chem. Soc, 127, pp. 10840-10841 
504 |a Prechtl, M.H.G., Hölscher, M., Ben-David, Y., Theyssen, N., Loschen, R., Milstein, D., Leitner, W., (2007) Angew. Chem., Int. Ed, 46, pp. 2269-2272 
504 |a Feller, M., Ben-Ari, E., Gupta, T., Shimon, L.J.W., Leitus, G., Diskin-Posner, Y., Weiner, L., Milstein, D., (2007) Inorg, Chem, 46, pp. 10479-10490 
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504 |a The two bands are a solid state effect, as only one band is observed in solution (see Table 4). Note that the linear nitrosyl CoCl2(NO) (PMePh2)2 was reported to be partially transformed to the bent nitrosyl isomer by grinding in preparation for a Nujol mull, resulting in two IR absorption bands: see ref 4a; Richter-Addo, G.B., Wheeler, R.A., Hixson, C.A., Chen, L., Khan, M.A., Ellison, M.K., Schulz, C.E., Scheidt, R., (2001) J. Am. Chem. Soc, 123, pp. 6314-6326 
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504 |a Immoos, C. E.; Sulc, F.; Farmer, P. J.; Czarnecki, K.; Bocian, D. F.; Levina. A.; Aitken, J. B.; Armstrong, R. S.; Lav. P. A. 7. Am. Chem. Soc. 2005, 127, 814-815; Wyllie, G.R.A., Scheidt, W.R., (2002) Chem. Rev, 102, pp. 1067-1089 
504 |a Haymore, B.L., Ibers, J.A., (1975) Inorg. Chem, 14, pp. 3060-3070 
504 |a Herde, J.L., Senoff, C.V., (1971) Inorg. Nucl. Chem. Lett, 7, pp. 1029-1031 
504 |a Connelly, N.G., Draggett, P.T., Green, M., Kuc, T.A., (1977) J. Chem. Soc. Dalton Trans, pp. 70-73 
520 3 |a Pincer-type linear nitrosyl Rh(I) complexes, Rh(PCPBu)(NO)][BF4] (2) and [Rh(PCPBuCH2)(NO)][BF,4] (8), are reported (PCPBu = 1,3-bis[(di-fer/-butylphosphino)methyl]-2,4,6-trimethylbenzene). Complex 2 was synthesized by reaction of the Rh(I) dinitrogen complex Rh(PCPBu)N 2 (1) with NOBF2, while treatment of the methyl chloride complex Rh(PCPBu)(CH3)Cl (7) with NOBF4 led to the formation of 8. Upon addition of CO, a linear bent nitrosyl equilibrium was established, both in solution and in the solid state, between the linear nitrosyl Rh(I) complex 2 and the bent nitrosyl Rh(III) complex [Rh(PCP'Bu)(NO)(CO)][BF4] (3). Addition of LiCl to complex 2 resulted in the quantitative formation of the bent nitrosyl complex Rh(PCPBu)(NO)(Cl) (4). An IR study of solvent interactions of the nitrosyl ligand of complex 2 in various solvents is also presented, showing a linear bent nitrosyl equilibrium induced by solvent coordination. Treatment of 4 with HBF4 · O(C2H5)2 led to chloride abstraction, with formation of complex 2. Upon addition of NOBF4 to the PNP Rh(I) complex [C5HN(CH2P- (tBu)2) 2Rh(CH3CN)]BF4 (5), the bent nitrosyl complex C5H3N(CH2P(tBu)2) 2Rh(CH3CN)(NO)][BF4]2 (6) was obtained. Employing 15NO-labeled complexes it is possible to assign the bent or linear modes of bonding of NO on the basis of 15N NMR spectroscopy. X-ray structures of all nitrosyl complexes reported here confirm that the tetracoordinate species are square-planar with a linear nitrosyl ligand occupying the position trans to the aromatic ring and the metal is Rh(I), whereas the pentacoordinate complexes adopt a square-pyramidal geometry with a bent apical nitrosyl coordinated to Rh(III).© 2009 American Chemical Society.  |l eng 
593 |a Departamento de Química Inorgánica, Analítica y Química Física/INQUIMAE-CONICET, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón II, Piso 3, (C1428EHA) Buenos Aires, Argentina 
593 |a Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Spain 
593 |a Department of Chemical Research Support, Weizmann Institute of Science, Rehovot, 76100, Spain 
690 1 0 |a AROMATIC RINGS 
690 1 0 |a CHLORIDE ABSTRACTIONS 
690 1 0 |a DINITROGEN COMPLEXES 
690 1 0 |a LINEAR MODES 
690 1 0 |a METHYL CHLORIDES 
690 1 0 |a NITROSYL COMPLEXES 
690 1 0 |a NMR SPECTROSCOPIES 
690 1 0 |a PENTACOORDINATE COMPLEXES 
690 1 0 |a QUANTITATIVE FORMATIONS 
690 1 0 |a RH COMPLEX 
690 1 0 |a RHODIUM COMPLEXES 
690 1 0 |a SOLVENT COORDINATIONS 
690 1 0 |a SOLVENT INTERACTIONS 
690 1 0 |a SQUARE-PYRAMIDAL GEOMETRIES 
690 1 0 |a TRIMETHYLBENZENE 
690 1 0 |a X-RAY STRUCTURES 
690 1 0 |a CHLORINE COMPOUNDS 
690 1 0 |a LIGANDS 
690 1 0 |a NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY 
690 1 0 |a RHODIUM 
690 1 0 |a SOLID SOLUTIONS 
690 1 0 |a SOLVENTS 
690 1 0 |a SYNTHESIS (CHEMICAL) 
690 1 0 |a RHODIUM COMPOUNDS 
700 1 |a Ben-David, Y. 
700 1 |a Shimon, L.J.W. 
700 1 |a Doctorovich, F. 
700 1 |a Milstein, D. 
773 0 |d 2009  |g v. 28  |h pp. 1917-1926  |k n. 6  |p Organometallics  |x 02767333  |w (AR-BaUEN)CENRE-2351  |t Organometallics 
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856 4 0 |u https://hdl.handle.net/20.500.12110/paper_02767333_v28_n6_p1917_Gaviglio  |y Handle 
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