Silyl complexes of molybdenum and tungsten - Synthesis, reactivity and structure

Petri SHA, Neumann B, Stammler H-G, Jutzi P (1998)
JOURNAL OF ORGANOMETALLIC CHEMISTRY 553(1-2): 317-329.

Zeitschriftenaufsatz | Veröffentlicht | Englisch
 
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Abstract / Bemerkung
The photochemical reaction of Cp2MH2 (M = Mo, 1; W, 2) with several hydridosilanes HSiR3 produces the corresponding silyl hydride complexes Cp2M(H)(SiR3) (M=Mo: SiR3=SiEt3, 3; SiCl3, 4; Si(OEt)(3), 5; SiH2(C5Me5), 6; SiH2(C5Me4H)(2), 7; SiH(C5Me4H)(2), 8; SiH2[2-(Me2NCH2)C6H4], 9; M = W: SiR3=SiCl3, 10) by a reductive elimination/oxidative addition process. Analogous photolysis of 1 in the presence of (C5Me5)(2)SiHCl or (C5Me5)(2)SiH2 does not yield the corresponding complexes Cp2Mo(H)(SiR3) (SiR3=SiCl(C5Me5)(2); SiH(C5Me5)(2)). Treatment of 4 and 6, respectively, with LiAlH4 leads to the hydridosilyl complex Cp2Mo(H)(SiH3) 11. Compounds 6-8 and 11 are expected to be single-source precursors for generation of molybdenum silicides. The hydride complexes 4, 5, and 6 are readily converted to the chloro compounds Cp2Mo(Cl)(SiR3) (SiR3=SiCl3, 12; Si(OEt)(3), 13; SiH2(C5Me5), 14). The reaction of 11 with CCl4 yields complex 12 under exchange of each non-C-bound hydrogen atom. Spectroscopic data of the metallosilanes are discussed and compared with the ones of the parent silanes. An intramolecular N-donor coordination of the functionalized aryl substituent is indicated for 9 by means of Si-29 NMR spectroscopy. 6 undergoes fast sigmatropic rearrangements within the Si-(C5Me5) fragment as proved by a variable temperature H-1 NMR investigation. The structures of 6, 7, 8, and 12 have been determined by single-crystal X-ray diffractometry. Bonding parameters of these typical bent-sandwich complexes are discussed taking account of electronic and steric influences.
Stichworte
single-source precursor; silyl; molybdenum; Tungsten; X-ray diffraction
Erscheinungsjahr
1998
Zeitschriftentitel
JOURNAL OF ORGANOMETALLIC CHEMISTRY
Band
553
Ausgabe
1-2
Seite(n)
317-329
ISSN
0022-328X
Page URI
https://pub.uni-bielefeld.de/record/1625489

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Petri SHA, Neumann B, Stammler H-G, Jutzi P. Silyl complexes of molybdenum and tungsten - Synthesis, reactivity and structure. JOURNAL OF ORGANOMETALLIC CHEMISTRY. 1998;553(1-2):317-329.
Petri, S. H. A., Neumann, B., Stammler, H. - G., & Jutzi, P. (1998). Silyl complexes of molybdenum and tungsten - Synthesis, reactivity and structure. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 553(1-2), 317-329. https://doi.org/10.1016/S0022-328X(97)00617-7
Petri, SHA, Neumann, B, Stammler, Hans-Georg, and Jutzi, Peter. 1998. “Silyl complexes of molybdenum and tungsten - Synthesis, reactivity and structure”. JOURNAL OF ORGANOMETALLIC CHEMISTRY 553 (1-2): 317-329.
Petri, S. H. A., Neumann, B., Stammler, H. - G., and Jutzi, P. (1998). Silyl complexes of molybdenum and tungsten - Synthesis, reactivity and structure. JOURNAL OF ORGANOMETALLIC CHEMISTRY 553, 317-329.
Petri, S.H.A., et al., 1998. Silyl complexes of molybdenum and tungsten - Synthesis, reactivity and structure. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 553(1-2), p 317-329.
S.H.A. Petri, et al., “Silyl complexes of molybdenum and tungsten - Synthesis, reactivity and structure”, JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 553, 1998, pp. 317-329.
Petri, S.H.A., Neumann, B., Stammler, H.-G., Jutzi, P.: Silyl complexes of molybdenum and tungsten - Synthesis, reactivity and structure. JOURNAL OF ORGANOMETALLIC CHEMISTRY. 553, 317-329 (1998).
Petri, SHA, Neumann, B, Stammler, Hans-Georg, and Jutzi, Peter. “Silyl complexes of molybdenum and tungsten - Synthesis, reactivity and structure”. JOURNAL OF ORGANOMETALLIC CHEMISTRY 553.1-2 (1998): 317-329.
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