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Dinitrogenvanadates(-1): Synthesis, Reactions and Conditions for their Stability

DOI: 10.1039/DT9940003471

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 3471 - 3478 (1994)

Update date:2022-09-26

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Authors:

Gailus, HartmutGailus, Hartmut

Woitha, ClausWoitha, Claus

Rehder, DieterRehder, Dieter

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Article abstract of DOI:10.1039/DT9940003471

Reduction of by Na or Li (M) in the presence of phosphines (Lm) and N2 yielded the complexes Na (n = 1 or 2), M2(4-n)> 2 = Me2PCH2CH2PMe2 (dmpe) or Ph2PCH2CH2PPh2>, Na3> 3 = PhP<(CH2)2PPh2>2, MeP<(CH2)3PMe2>2 (bdmpm) or MeP<(CH2)3PEt2>2> and Na4> 4 = P<(CH2)2PPh2>3, P<(CH2)3PMe2>3 or P<(CH2)3PEt2>3>.Generally, the complexes are labile, with a maximum stability for cis- and trans-M.In the presence of CO or CN-t-Bu, N2 is replaced by these ligands.The compounds have been characterized by their ν(NN) pattern and by 51V; 23Na and 7Li NMR spectroscopy.The 51 V NMR spectra exhibit well resolved multiplets.All spectroscopic data, in particular 7Li NMR of cis- and trans- in tetrahydrofuran, are indicative of close contact ion-pair interaction of the kind V-NN...M(1+).The potassium ion and large cations such as (1+) do not provide stable complexes, and complexation of Li(1+) and Na(1+) by crown ethers leads to immediate decomposition of the N2 complexes.The reductive protonation of part of the co-ordinated N2 to NH4(1+) (plus small amounts of N2H5(1+)) is discussed in term of similar reactivity features to the analogous complexes, and in the context of these N2 complexes as functional models for nitrogenases.The compound , isolated as an intermediate product of the reduction of VCl3, reacted with LiNHNH2 to yield ammonia.

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Product name:Na(1+)*V(N2)((CH3)2PCH2CH2P(CH3)2)(C6H5P((CH2)2P(C6H5)2)2)(1-)=Na[V(N2)((CH3)2PCH2CH2P(CH3)2)(C6H5P((CH2)2P(C6H5)2)2)]

Cas No:160361-54-6

160361-54-6

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