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Structural Reorganizations accompanying the Nickel(II)-Nickel(I) Redox change in Nickel Complexes with the Tripodal Ligand MeC(CH2PPh2)3(Triphos, L). X-Ray Crystal Structure of

DOI: 10.1039/DT9900003761

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 3761 - 3766 (1990)

Update date:2022-08-04

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Authors:

Zanello, PieroZanello, Piero

Cinquantini, ArnaldoCinquantini, Arnaldo

Ghilardi, Carlo A.Ghilardi, Carlo A.

Midollini, StefanoMidollini, Stefano

Moneti, SimonettaMoneti, Simonetta

et al.et al.

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Article abstract of DOI:10.1039/DT9900003761

The stereodynamic aspects of the nickel(II)-nickel(I) conversion in complexes of the tridentate phosphine MeC(CH2PPh2)3, (triphos, L) have been analysed.The structural reorganization, which accompanies the redox change, is pointed out.The substantial electrochemical reversibility observed for the nickel(II)-nickel(I) reduction, being indicative of minor molecular rearrangement, is consistent with the simple elongation of the Ni-I bond distance in the nickel(I) with respect to the nickel(II) derivative <2.546(2) vs. 2.414(4) Angstroem>.The nickel(II) complexes Y (X=Cl, Br, or I, Y=ClO4) and 2 have been synthetized and characterized.A complete X-ray analysis has been carried out for 2. a=22.500(8), b=19.092(5), c=24.912(12) Angstroem, β=109.29(4) deg, space group C2/c, Z=4.The X-ray results showed two very interesting features: the isolation of a tetrahedral nickel(II) complex with the unprecendent P3X donor atom set and the formation of the new polyanionic cluster species 2-.An angular overlap model analysis was performed to rationalize the electronic spectra of the + complexes (X=Cl, Br, or I).

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