The reaction of a mixture of 1 equiv of PhPH2 and 2 equiv of PhNHSiMe2CH2Cl with 4 equiv of (BuLi)-Li-n followed by the addition of THF generates the lithiated ligand precursor [NPN]Li-2. (TKF)2(where [NPN] = PhP(CH2SiMe2NPh)(2)). The reaction of [NPN]Li-2. (THF)(2) with TaMe3Cl2 produces [NPN]TaMe3, which reacts under HZ to yield the diamagnetic dinuclear Ta(IV! tetrahydride ([NPN]Ta)(2)(mu -H)4 This hydride reacts with N-2 with the loss of H-2 to produce ([NPN]Ta(mu -H))(2)(mu-eta (1):eta (2)-N-2), which was characterized both in solution and in the solid state, and contains strongly activated Nz bound in the unprecedented side-on end-on dinuclear bonding mode. A density functional theory calculation on the model complex [(H3P)(H2N)(2)Ta(mu -H)](2)-mu-eta (1):eta (2)-N-2) provides insight into the molecular orbital interactions involved in the side-on end-on bonding mode of dinitrogen. The reaction of ([NPN]Ta(mu -H))(2)(mu-eta (1):eta (2)-N-2) with propene generates the end-on bound dinitrogen complex ([NPN]Ta(CH2CH2CH3))(2)(mu-eta (1):eta (1)-N-2), and the reaction of [NPN]Li-2. (THF)(2) with NbCl3-(DME) generates the end-on bound dinitrogen complex ([NPN]NbCl)(2)(mu-eta (1):eta (1)-N-2). These two end-on bound dinitrogen complexes provide evidence that the bridging hydride ligands are responsible for the unusual bonding mode of dinitrogen in ([NPN]Ta(mu -H))(2)(mu-eta (1):eta (2)-N-2). The dinitrogen moiety in the side-on end-on mode is amenable to functionalization; the reaction of ([NPN]Ta(mu -H))(2)(mu-eta (1):eta (2)-N-2) with PhCH2Br results in C-N bond formation to yield [NPN]Ta(mu-eta (1):eta (2)-N2CH2Ph)(mu -H)(2)TaBr[NPN]. Nitrogen-15 NMR spectral data an provided for all the tantalum-dinitrogen complexes and derivatives described.

New mode of coordination for the dinitrogen ligand: Formation, bonding, and reactivity of a tantalum complex with a bridging N-2 unit that is both side-on and end-on / M. Fryzuk, S. Johnson, B. Patrick, A. Albinati, S. Mason, T. Koetzle. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - 123:17(2001 May 02), pp. 3960-3973.

New mode of coordination for the dinitrogen ligand: Formation, bonding, and reactivity of a tantalum complex with a bridging N-2 unit that is both side-on and end-on

A. Albinati;
2001

Abstract

The reaction of a mixture of 1 equiv of PhPH2 and 2 equiv of PhNHSiMe2CH2Cl with 4 equiv of (BuLi)-Li-n followed by the addition of THF generates the lithiated ligand precursor [NPN]Li-2. (TKF)2(where [NPN] = PhP(CH2SiMe2NPh)(2)). The reaction of [NPN]Li-2. (THF)(2) with TaMe3Cl2 produces [NPN]TaMe3, which reacts under HZ to yield the diamagnetic dinuclear Ta(IV! tetrahydride ([NPN]Ta)(2)(mu -H)4 This hydride reacts with N-2 with the loss of H-2 to produce ([NPN]Ta(mu -H))(2)(mu-eta (1):eta (2)-N-2), which was characterized both in solution and in the solid state, and contains strongly activated Nz bound in the unprecedented side-on end-on dinuclear bonding mode. A density functional theory calculation on the model complex [(H3P)(H2N)(2)Ta(mu -H)](2)-mu-eta (1):eta (2)-N-2) provides insight into the molecular orbital interactions involved in the side-on end-on bonding mode of dinitrogen. The reaction of ([NPN]Ta(mu -H))(2)(mu-eta (1):eta (2)-N-2) with propene generates the end-on bound dinitrogen complex ([NPN]Ta(CH2CH2CH3))(2)(mu-eta (1):eta (1)-N-2), and the reaction of [NPN]Li-2. (THF)(2) with NbCl3-(DME) generates the end-on bound dinitrogen complex ([NPN]NbCl)(2)(mu-eta (1):eta (1)-N-2). These two end-on bound dinitrogen complexes provide evidence that the bridging hydride ligands are responsible for the unusual bonding mode of dinitrogen in ([NPN]Ta(mu -H))(2)(mu-eta (1):eta (2)-N-2). The dinitrogen moiety in the side-on end-on mode is amenable to functionalization; the reaction of ([NPN]Ta(mu -H))(2)(mu-eta (1):eta (2)-N-2) with PhCH2Br results in C-N bond formation to yield [NPN]Ta(mu-eta (1):eta (2)-N2CH2Ph)(mu -H)(2)TaBr[NPN]. Nitrogen-15 NMR spectral data an provided for all the tantalum-dinitrogen complexes and derivatives described.
transition-metal complexes; P2N2 = PHP(CH2SIME2NSIME2CH2)(2)PPH; X-ray structure; molecular-structures; nitrogen-fixation; crystal-structure; chemistry; cleavage; activation; compound
Settore CHIM/03 - Chimica Generale e Inorganica
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/256825
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