Substituent Effects in the Hydrosilylation of Coordinated Dinitrogen in a Ditantalum Complex: Cleavage and Functionalization of N2
In: Journal of the American Chemical Society, Jg. 128 (2006-06-30), S. 9472-9483
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Zugriff:
The dinitrogen complex ([NPN]Ta)2(mu-eta1:eta2-N2)(mu-H)2, 1, (where [NPN] = (PhNSiMe2CH2)2PPh) undergoes hydrosilylation with primary and secondary alkyl- and arylsilanes, giving a new N-Si bond and a new terminal tantalum hydride derived from one Si-H unit. Various primary silanes can be employed to give isolable complexes of the general formula ([NPN]TaH)(mu-N-N-SiH(n)R(3-n))(mu-H)2(Ta[NPN]) (5, R=Bu, n = 2; 9, R=Ph, n = 2). Analogous complexes featuring secondary silanes are not isolable, because these products, and 5 and 9, are uniformly unstable toward reductive elimination of bridging hydrides as H2, followed by cleavage of the N-N bond to give ([NPN]TaH)(mu-N)(mu-N-SiH(n)R(3-n))(Ta[NPN]) (6, R=Bu, n = 2; 10, R=Ph, n = 2; 15, R=Ph, n = 1; 16, R=Ph and Me, n = 1). The bridging nitrido ligand in these complexes is itself a substrate for a second hydrosilylation when n = 2, and schemes leading to Ta(IV) complexes of the general formula ([NPN]Ta)2(mu-N-SiH2R)(mu-N-SiH2R') via elimination of H2 are reported (4, R=R'=Bu; 12, R=Bu, R' = Ph; 13, R=Bu, R' = CH2CH2SiH3). At this point, the general reaction manifold for these compounds ramifies, with distinct outcomes occurring for different R groups-[NPN] ligand amide migration from Ta to RSi affords 11, whereas stable complex 6 rearranges to give 7, in the presence of excess silane. Ethanediylbissilane reacts with 1 to give 14, isostructural to 7.
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Substituent Effects in the Hydrosilylation of Coordinated Dinitrogen in a Ditantalum Complex: Cleavage and Functionalization of N2
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Autor/in / Beteiligte Person: | MacKay, Bruce A. ; Fryzuk, Michael D. ; Munhá, Rui F. |
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Zeitschrift: | Journal of the American Chemical Society, Jg. 128 (2006-06-30), S. 9472-9483 |
Veröffentlichung: | American Chemical Society (ACS), 2006 |
Medientyp: | unknown |
ISSN: | 1520-5126 (print) ; 0002-7863 (print) |
DOI: | 10.1021/ja061508q |
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