Unique Stable Organometalhc Nickel(III) Complexes: Syntheses and the Molecular Structure of Ni[C6H3(CH2NMe2)2-o,o]I2

Journal of the American Chemical Society

Volumn 105, Issue 5, 1983, Pages 1379-1380

  Grove, David M ^a   van Koten, Gerard ^a   Zoet, Rob ^a   Murrall, Nicholas W ^b   Welch, Alan J ^b  

^a UNIVERSITY OF AMSTERDAM   (Netherlands)

^b UNIVERSITY OF EDINBURGH   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001269493     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00343a056     Document Type: Article

References (20)

1. A fairly recent review covering this subject is given in the following: Lappert, M. F.; Lednor, P. Adv. Organomet. Chem. 1976, 14, 345-399.
2. Haines, R. I.; McAuley, A. Coord. Chem. Rev. 1981, 39, 77-119.
3. Nag, K.; Chakravorty, A. Coord. Chem. Rev. 1980, 33, 87-147.
4. The syntheses and characterization of these and related complexes will be the subject of a forthcoming publication.
5. Complex lb has also been isolated in low yield from the reaction of 2b with either Br2 or N-bromosuccinimide. The copper halide reactions were carried out in acetone, whereas benzene was used for the syntheses of lc.
6. 2: Evans, D. F. J. Chem. Soc. 1959, 2003. Loliger, J.; Scheffold, R. J. Chem. Educ. 1972, 49, 646.
7. The UV-visible spectra of these solutions show several absorption maxima between 300 and 750 nm with e values in the range 200-2000 L mol″1 cm″1.
8. For ESR data, complexes la-c are assumed to have a principal pseu-do-C2 axis colinear with the Ni apical halide bond, (g) values for la-c at room temperature are ca. 2.19, 2.17, and 2.14 respectively.
9. Although Cl has two isotopes with I = 3/2, it was not possible to detect their individual lines. However, Br with two isotopes (both I = 3/2) exhibits much larger spin-spin couplings, and resolution of the separate lines is to be anticipated. This together with the second-order complications makes extraction of accurate data for lb and lc nontrivial, and further work, including measurement of Q-band spectra, is in progress.
10. Sheldrick, G. M., University of Cambridge, 1976.
11. Full data and other details will be published elsewhere (N.W.M. and A.J.W.).
12. Defined by the atoms Cl, NI, N2, and 12.
13. Grove, D. M.; van Koten, G.; Zoet, R.; Spek, A. L., to be submitted for publication.
14. Stalik, J. K.; Ibers, J. A. Inorg. Chem. 1970, 9, 453-458.
15. These conclusions are in line with those of other workers involved with Ni(III) complexes and in particular the published data for [NiBr(l, 4, 8,11-tetraazacyclotetradecane)]2+ bear close comparison. Desideri, A.; Raynoor, J. B.; Poon, C.-K. J. Chem. Soc, Dalton Trans. 1977, 2051-2054.
16. The shortest mutual contact is H(93)-H(lll) at 2.93 A.
17. 2 electrode. The potential was measured at +0.24 V in acetone by using 0.1 M Bu4NBr as base electrolyte with Pt electrodes referred to an Ag/AgCl (0.1 M LiCl in acetone) reference electrode. See: Bond, A. M.; Hendrickson, A. F.; Martin, R. L. J. Am. Chem. Soc. 1973, 95, 1449-1456.
18. In this complex the heterobimetallic interaction is donative from Pt(II) to Hg(II) but nevertheless results in a similar terdentate ligand conformation and metal coordination geometry as that found in lc: van der Ploeg, A. F. M. J.; van Koten, G.; Vrieze, K.; Spek, A. L.; Duisenberg, A. J. M. Organometallics 1982, 1, 1366.
19. Terheijden, J.; van Koten, G.; Ubbels, H.J.C. manuscript in preparation.
20. 2-o, o)BrCl, which has been separately synthesized and characterized. Its presence was due to a contamination of a sample of 2a by 2b.