Issue 31, 2007
From the journal:

Dalton Transactions

Crystal structures and solution behaviors of dinuclear d10-metal complexes containing anions of N,N′-bis(pyrimidine-2-yl)formamidine†

Zhi-Kai Chan,a   Tsun-Ren Chen,b   Jhy-Der Chen,*a   Ju-Chun Wangc  and  C. W. Liud  

* Corresponding authors

a Department of Chemistry, Chung-Yuan Christian University, Chung-Li, Taiwan, R.O.C

b Department of Applied Chemistry and Life Sciences, National Pingtung University of Education, PingTung, Taiwan, R.O.C

c Department of Chemistry, Soochow University, Taipei, Taiwan, R. O. C

d Department of Chemistry, National Dong Hwa University, Hualien, Taiwan, R. O. C

Abstract

The salts of Zn(II), Cd(II) and Hg(II) react instantaneously with Kpmf (pmf− = anion of N,N′-bis(pyrimidine-2-yl)formamidine, Hpmf) in THF, producing bimetallic complexes of the types [M2(pmf)3](X) (M = Zn(II), X = I3−, 1a; M = Zn(II), X = NO3−, 1b; M = Zn(II), X = ClO4−, 1c; M = Cd(II), X = NO3−, 2a; M = Cd(II), X = ClO4−, 2b) and Hg2(pmf)2X2 (X = Cl, 3a; Br, 3b; I, 3c). New tridentate and tetradentate coordination modes were observed for the pmf− ligands and their fluxional behaviors investigated by measuring variable-temperature 1H NMR spectra. Complexes 2a and 2b, which possess only tetradentate coordination modes for the pmf− ligands in the solid state show larger free energy of activation (ΔGc≠) for the exchange than complexes 1a–c and 3a–c with tetradentate and/or tridentate coordination modes. Complexes 1a–c and 3a–c are the first dinuclear Zn(II) and Hg(II) complexes containing formamidinate ligands. Moreover, the separation between the two Hg(II) atoms are 3.4689(9), 3.4933(13) and 3.5320(10) Å for complexes 3a–c, respectively, similar to the sum of van der Waals radii of two Hg(II) atoms which is 3.50(7) Å. All the complexes exhibit emissions and the nature of the anions hardly change the emission wavelengths of the complexes with the same metal centers. The emission bands may be tentatively assigned as intraligand (IL) π → π* transitions.

Graphical abstract: Crystal structures and solution behaviors of dinuclear d10-metal complexes containing anions of N,N′-bis(pyrimidine-2-yl)formamidine

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Article information

DOI
https://doi.org/10.1039/B703727A
Article type
Paper
Submitted
23 Mar 2007
Accepted
17 May 2007
First published
15 Jun 2007

Dalton Trans., 2007, 3450-3458

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Crystal structures and solution behaviors of dinuclear d10-metal complexes containing anions of N,N′-bis(pyrimidine-2-yl)formamidine

Z. Chan, T. Chen, J. Chen, J. Wang and C. W. Liu, Dalton Trans., 2007, 3450 DOI: 10.1039/B703727A

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