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Volumn 27, Issue 7, 2008, Pages 1617-1625

Bis(cyclopentadienyl)phenylphosphine as ligand precursor for assembling heteropolymetal complexes

Author keywords

[No Author keywords available]

Indexed keywords

COMPLEXATION; LITHIUM COMPOUNDS; REACTION KINETICS; SPECTROSCOPIC ANALYSIS;

EID: 42449089323     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om701221p     Document Type: Article
Times cited : (3)

References (56)
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    • For different use of cyclopentadienyls and other aromatic units containg either alkylene or alkenylene spacers and a variety of heteroatomcentered groups based on B, Ge, Si, Sn, P, As, and S, see also: (a) Lee, I.; Dahan, F.; Maisonnat, A.; Poilblanc, R. Organometallics 1994, 13, 2743.
    • For different use of cyclopentadienyls and other aromatic units containg either alkylene or alkenylene spacers and a variety of heteroatomcentered groups based on B, Ge, Si, Sn, P, As, and S, see also: (a) Lee, I.; Dahan, F.; Maisonnat, A.; Poilblanc, R. Organometallics 1994, 13, 2743.
  • 35
    • 0001564410 scopus 로고    scopus 로고
    • 4) (Butler, I. R.; Cullen, W. R.; Rettig, S. J. Organometallics 1987, 6, 872) as the main product.
    • 4) (Butler, I. R.; Cullen, W. R.; Rettig, S. J. Organometallics 1987, 6, 872) as the main product.
  • 36
    • 0039253109 scopus 로고    scopus 로고
    • Although 31P NMR analysis of a sample of crude reaction mixture clearly indicated the complete and exclusive formation of 9 and 10, the subsequent chromatographic purification always produced three different products. The first eluted band (deep red) gave, after solvent evaporation, a small amount of a dark solid whose characterization is still under investigation. The second eluted fraction (red) was identified as the expected product, and the third (purple) fraction after evaporation of the solvent gave a red-purple solid that was identified by NMR spectroscopy and mass spectroscopy as the dimeric complex (Shin, J. H, Parkin, G. Inorg. Chem. Commun. 1999, 2, 428) represented in the following structure
    • 31P NMR analysis of a sample of crude reaction mixture clearly indicated the complete and exclusive formation of 9 and 10, the subsequent chromatographic purification always produced three different products. The first eluted band (deep red) gave, after solvent evaporation, a small amount of a dark solid whose characterization is still under investigation. The second eluted fraction (red) was identified as the expected product, and the third (purple) fraction after evaporation of the solvent gave a red-purple solid that was identified by NMR spectroscopy and mass spectroscopy as the dimeric complex (Shin, J. H.; Parkin, G. Inorg. Chem. Commun. 1999, 2, 428) represented in the following structure.
  • 39
    • 0004204702 scopus 로고
    • 2nd ed, Clarendon Press: Oxford, U.K
    • Emsley, J. The Elements, 2nd ed.; Clarendon Press: Oxford, U.K., 1991.
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    • Emsley, J.1
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    • 2 (13) as side product in the oxidative addition of zerovalent palladium has been reported: Weigelt, M.; Becher, D.; Poetsch, E.; Bruhn, C.; Steinborn, D. Z. Anorg. Allg. Chem. 1999, 625, 1542.
    • 2 (13) as side product in the oxidative addition of zerovalent palladium has been reported: Weigelt, M.; Becher, D.; Poetsch, E.; Bruhn, C.; Steinborn, D. Z. Anorg. Allg. Chem. 1999, 625, 1542.
  • 43
    • 42449151918 scopus 로고    scopus 로고
    • 31P) spectra with the aid of computer simulation, using the gNMR program. See: Budzelaar, P. H. M. gNMR, V4.0; Cherwell Scientific Publishing, Copyright Iviry soft, 1995-1997.
    • 31P) spectra with the aid of computer simulation, using the gNMR program. See: Budzelaar, P. H. M. gNMR, V4.0; Cherwell Scientific Publishing, Copyright Iviry soft, 1995-1997.
  • 46
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    • While observation of 13 was retained perfectly coherent with formation of 11 (Scheme 2, its occurrence seemed to rule out formation of 14. To force formation of 11 we used a twofold excess of Pd(PPh3)4. One equivalent of Pd would be necessary to form the Bimetallic array Mo-Pd-Mo of 11, while the second equivalent was expected to extract the two iodine groups from 9 with formation of 13. Moreover, it is worthy of note to underline variations of oxidation numbers of metal centers taking place in the transformations outlined in Scheme 2. Upon formation of 11 and 12 the molybdenum and tungsten atoms of 9 and 10 are reduced from the initial oxidation numbers +2 into +1. Conversely, while the zerovalent palladium entering into 9 and 10 to form 11 and 12 maintains its zero oxidation number, the palladium forming trans-(PPh3)2PdI2 is oxidized from Pd(O) to Pd+2
    • 2 is oxidized from Pd(O) to Pd(+2).
  • 48
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    • 3 in a 1:2 stoichiometric ratio.
    • 3 in a 1:2 stoichiometric ratio.
  • 52
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    • 3 from the W analogue is more difficult, thus chromatographic purification affording pure 15 is possible.
    • 3 from the W analogue is more difficult, thus chromatographic purification affording pure 15 is possible.
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    • Kluver Academic: Dordrecht, The Netherlands, The Netherlands
    • Wilson. A. J.C. International Tables for X-Ray Crystallography; Kluver Academic: Dordrecht, The Netherlands, The Netherlands, 1992; Vol. C, p 500.
    • (1992) International Tables for X-Ray Crystallography , vol.100 , pp. 500
    • Wilson, A.J.C.1
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    • Sheldrick, G. M. SHELX-97. Program for Structure Refinement, Release 97-2; University of Göttingen: Göttingen, Germany, 1997.
    • Sheldrick, G. M. SHELX-97. Program for Structure Refinement, Release 97-2; University of Göttingen: Göttingen, Germany, 1997.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.