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Abstract:

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.

Registro:

Documento: Artículo
Título:Synthesis, structure, and reactivity of nitrosyl pincer-type rhodium complexes
Autor:Gaviglio, C.; Ben-David, Y.; Shimon, L.J.W.; Doctorovich, F.; Milstein, D.
Filiación:Departamento de Química Inorgánica, Analítica y Química Física/INQUIMAE-CONICET, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón II, Piso 3, (C1428EHA) Buenos Aires, Argentina
Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Spain
Department of Chemical Research Support, Weizmann Institute of Science, Rehovot, 76100, Spain
Palabras clave:Aromatic rings; Chloride abstractions; Dinitrogen complexes; Linear modes; Methyl chlorides; Nitrosyl complexes; Nmr spectroscopies; Pentacoordinate complexes; Quantitative formations; Rh complex; Rhodium complexes; Solvent coordinations; Solvent interactions; Square-pyramidal geometries; Trimethylbenzene; X-ray structures; Chlorine compounds; Ligands; Nuclear magnetic resonance spectroscopy; Rhodium; Solid solutions; Solvents; Synthesis (chemical); Rhodium compounds
Año:2009
Volumen:28
Número:6
Página de inicio:1917
Página de fin:1926
DOI: http://dx.doi.org/10.1021/om8011536
Título revista:Organometallics
Título revista abreviado:Organometallics
ISSN:02767333
CODEN:ORGND
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_02767333_v28_n6_p1917_Gaviglio

Referencias:

  • Machura, B., (2005) Coord. Chem. Rev, 249, pp. 2277-2307
  • Coppens, P.; Novozhilova. 1.; Kovalevsky, A. Chem. Rev. 2002, 102, 861- 884; Roncaroli, F., Videla, M., Slep, L.D., Olabe, J.A., (2007) Coord. Chem. Rev, 251, pp. 1903-1930
  • Richter-Addo, G.B., Legzdins, P., (1992) Metals Nitrosyls, , Oxford University Press: New York
  • Enemark, J.H., Feltham, R.D., (1974) Coord. Chem. Rev, 13, pp. 339-406
  • Enemark, J.H., Feltham, R.D., (1981) Top. Stereochem, 12, pp. 155-215
  • For early examples of equilibria between linear and bent nitrosyl complexes, see; Pratt Brock, C., Collman, J.P., Dolcetti, G., Farnham, P.H., Ibers, J.A., Lester, J.E., Reed, C.A., (1973) Inorg, Chem, 12, pp. 1304-1313
  • Schoonover, M.W., Baker, E.C., Eisenberg, R., (1979) J. Am. Chem. Soc, 101, pp. 1880-1882
  • Mason, J., Mingos, D.M.P., Sherman, D., Wardle, R.W.M., (1984) J. Chem. Soc, Chem. Commun, 122, pp. 3-1225
  • Hayton, W.T., Legzdins, P., Sharp, W.B., (2002) Chem. Rev, 102, pp. 935-991
  • McCleverty, J.A., (2004) Chem. Rev, 104, pp. 403-418
  • Miranda, K.M., (2005) Coord. Chem. Rev, 249, pp. 433-155
  • Pugh, D., Danopoulos, A.A., (2007) Coord. Client. Rev, 251, pp. 610-641. , Reviews: a
  • Szabó, K.J., (2006) Synlett, 6, pp. 811-824
  • Rybtchinski, B., Milstem, D., (2004) ACS Symp. Ser, 885, pp. 70-85
  • van der Boom, M.E., Milstein, D., (2003) Chem. Rev, 103, pp. 1759-1792
  • Singleton, J.T., (2003) Tetrahedron, 59, pp. 1837-1857
  • Milstein, D., (2003) Pure Appl. Chem, 75, pp. 445-460
  • Albrecht, M., van Koten, G., (2001) Angew. Chem., Int. Ed, 40, pp. 3750-3781
  • Vigalok, A., Milstein, D., (2001) Acc. Chem. Res, 34, pp. 798-807
  • Jensen, C.M., (1999) Chem. Commun, pp. 2443-2449
  • Rybtchinski, B., Milstein, D., (1999) Angew. Chem., Int. Ed, 38, pp. 870-883
  • Rvbtchinsky, B., Vigalok, A., Ben-David, Y., Milstein, D., (1996) J. Am. Chem. Soc, 1 I8, pp. 12406-12415
  • Gupta, M., Hagen, C., Elesher, R., Kaska, W.C., Jensen, C.M., (1996) Chem. Commun, p. 2083
  • Xu, W.W., Rosini, G.P., Krogh-Jespersen, K., Goldman, A.S., Gupta, M., Jensen, C.M., Kaska, W.C., (1997) Chem. Commun, pp. 2273-2274
  • Liu, F., Goldman, A.S., (1999) Chem. Commun, p. 655
  • Renkema, K.B., Kissin, Y.V., Goldman, A.S., (2003) J. Am. Chem. Soc, 125, p. 7770
  • Morales-Morales, D., Lee, D.W., Wang, Z., Jensen, C.M., (2001) Organometallics, 20, p. 1144
  • Haenel, M.W., Oevers, S., Angermund, K., Kaska, W.C., Fan, H.J., Hall, M.B., (2001) Angew. Chem, 113, p. 3708
  • (2001) Angew. Chem., Int. Ed, 40, p. 3596
  • Gottker- Schnetmann, I., White, P.S., Brookhart, M., (2004) J. Am. Chem. Soc, 126, p. 1804
  • Hermann, D., Gandelman, M., Rozenberg, H., Shimon, L.J.W., Milstein, D., (2002) Organometallics, 21, pp. 812-818
  • Ben-Ari, E., Gandelman, M., Rozenberg, H., Shimon, L.J.W., Milstein, D., (2003) J. Am. Chem. Soc, 125, pp. 4714-4715
  • Ben-Ari, E., Gandelman, M., Shimon, L.J.W., Martin, J.M.L., Milstein, D., (2006) Organometallics, 25, pp. 3190-3210
  • Feller, M., Karton, A., Leitus, G., Martin, J.M.L., Milstein, D., (2006) J. Am. Chem. Soc, 128, pp. 12400-12401
  • Ben-Ari, E., Leitus, G., Schimon, L.J.W., Milstem, D., (2006) J. Am. Chem. Soc, 128, pp. 15390-15391
  • Zhang, J., Gandelman, M., Shimon, L.J.W., Milstein, D., (2004) Oreanometallics, 23, pp. 4026-4033
  • Zhang, J., Leitus, G., Ben-David, Y., Milstein, D., (2005) J. Am. Chem. Soc, 127, pp. 10840-10841
  • 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
  • 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
  • Böttcher, K., Mereiter, K., (2004) Inorg. Chem. Commun, 7, pp. 1225-1228
  • Kelly, B.A., Welch, A.J., Woodward, P., (1977) J. Chem. Soc., Dalton Trans, p. 2237
  • Goldberg, S.Z., Kubiak, C., Meyer, C.D., Eisenberg, R., (1975) Inorg. Chem, 14, pp. 1650-1654
  • Choualeb, A., Lough, A.J., Gusev, S.G., (2007) Organometallics, 26, pp. 3509-3515
  • Vigalok, A., Milstein, D., (2000) Organometallics, 19, pp. 2061-2064
  • Bell, L.K., Mason, J., Mingos, D.M.P., Tew, D.G., (1983) Inorg. Chem, 22, pp. 3497-3502
  • Mason, J., Larkworthy, L.F., Moore, E.A., (2002) Chem. Rev, 102, pp. 913-934
  • 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
  • Evans, W., Zink (1981) J. Am. Chem. Soc, 103, pp. 2635-2640
  • Kosower, E.M., (1958) J. Am. Chem. Soc, SO, pp. 3253-3260
  • Vigalok, A., Rybtchinski, B., Shimon, L.J.W., Ben-David, Y., Milstein, D., (1999) Organometallics, 18, pp. 895-905
  • 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
  • Haymore, B.L., Ibers, J.A., (1975) Inorg. Chem, 14, pp. 3060-3070
  • Herde, J.L., Senoff, C.V., (1971) Inorg. Nucl. Chem. Lett, 7, pp. 1029-1031
  • Connelly, N.G., Draggett, P.T., Green, M., Kuc, T.A., (1977) J. Chem. Soc. Dalton Trans, pp. 70-73

Citas:

---------- APA ----------
Gaviglio, C., Ben-David, Y., Shimon, L.J.W., Doctorovich, F. & Milstein, D. (2009) . Synthesis, structure, and reactivity of nitrosyl pincer-type rhodium complexes. Organometallics, 28(6), 1917-1926.
http://dx.doi.org/10.1021/om8011536
---------- CHICAGO ----------
Gaviglio, C., Ben-David, Y., Shimon, L.J.W., Doctorovich, F., Milstein, D. "Synthesis, structure, and reactivity of nitrosyl pincer-type rhodium complexes" . Organometallics 28, no. 6 (2009) : 1917-1926.
http://dx.doi.org/10.1021/om8011536
---------- MLA ----------
Gaviglio, C., Ben-David, Y., Shimon, L.J.W., Doctorovich, F., Milstein, D. "Synthesis, structure, and reactivity of nitrosyl pincer-type rhodium complexes" . Organometallics, vol. 28, no. 6, 2009, pp. 1917-1926.
http://dx.doi.org/10.1021/om8011536
---------- VANCOUVER ----------
Gaviglio, C., Ben-David, Y., Shimon, L.J.W., Doctorovich, F., Milstein, D. Synthesis, structure, and reactivity of nitrosyl pincer-type rhodium complexes. Organometallics. 2009;28(6):1917-1926.
http://dx.doi.org/10.1021/om8011536