[en] Five complexes with the generic formula fac-[MnBr(CO)3(S2C[middle dot]NHC)] were obtained by reacting [MnBr(CO)5] with a set of representative imidazol(in)ium-2-dithiocarboxylate zwitterions. These ligands are the adducts of N-heterocyclic carbenes (NHCs) and carbon disulfide. The mononuclear Mn(i) derivatives were coupled with Na[Mn(CO)5] to afford bimetallic [Mn2(CO)6(S2C[middle dot]NHC)] clusters. Yet, the most convenient strategy to access these dinuclear Mn(0) products implied a direct carbonyl substitution from the [Mn2(CO)10] dimer. The molecular structures of three monometallic and four bimetallic compounds were elucidated by single crystal X-ray diffraction analysis. In the monometallic complexes, the NHC[middle dot]CS2 ligands exhibited a bidentate [small kappa]2-S,S[prime or minute] coordination mode with an S-C-S bite angle of about 116[degree]. In the dinuclear clusters, the CS2- unit acted as a chelate toward one manganese center and as a pseudoallylic ligand toward the other one. The S-C-S bite angle was reduced to ca. 104[degree]. Thus, the zwitterions displayed a remarkable flexibility, which also permitted a staggered arrangement of the carbonyl groups in the bimetallic systems. Examination of the [small nu, Greek, macron]CO absorption bands on IR spectroscopy helped identify the presence of fac-Mn(CO)3 or Mn2(CO)6 motifs, while the 13C NMR chemical shift of the CS2- moiety was a reliable indicator for monitoring its hapticity. Whereas the dinuclear clusters were air- and moisture-stable crystalline solids, mononuclear halido derivatives displayed only a limited stability under aerobic conditions. Both types of compounds underwent rather unselective, extensive fragmentations in the gas phase, in sharp contrast with the analogous rhenium derivatives that led to clean sequential decarbonylation processes upon collision-induced dissociation.
Disciplines :
Chemistry
Author, co-author :
Beltran Alvarez, Tomás Francisco ; Université de Liège > Département de chimie (sciences) > Chimie organométallique et catalyse homogène
Zaragoza, Guillermo
Delaude, Lionel ; Université de Liège > Département de chimie (sciences) > Chimie organométallique et catalyse homogène
Language :
English
Title :
Mono- and bimetallic manganese-carbonyl complexes and clusters bearing imidazol(in)ium-2-dithiocarboxylate ligands
Publication date :
2017
Journal title :
Journal of the Chemical Society. Dalton Transactions
ISSN :
1472-7773
eISSN :
1364-5447
Publisher :
Royal Society of Chemistry, Cambridge, United Kingdom
Coucouvanis, D., (1970) Progress in Inorganic Chemistry, 11, pp. 233-371. , ed. S. J. Lippard, John Wiley & Sons, Hoboken, NJ
Eisenberg, R., (1970) Progress in Inorganic Chemistry, 12, pp. 295-369. , ed. S. J. Lippard, John Wiley & Sons, Hoboken, NJ
Coucouvanis, D., (1979) Progress in Inorganic Chemistry, 26, pp. 301-469. , ed. S. J. Lippard, John Wiley & Sons, Hoboken, NJ
Burns, R.P., McCullough, F.P., McAuliffe, C.A., (1980) Advances in Inorganic Chemistry and Radiochemistry, 23, pp. 211-280. , ed. H. J. Emeléus and A. G. Sharpe, Academic Press, New York, NY
Hogarth, G., (2005) Progress in Inorganic Chemistry, 53, pp. 71-561. , ed. K. D. Karlin, John Wiley & Sons, Hoboken, NJ
Tiekink, E.R.T., Haiduc, I., (2005) Progress in Inorganic Chemistry, 54, pp. 127-319. , ed. K. D. Karlin, John Wiley & Sons, Hoboken, NJ
Galindo, A., Miguel, D., Perez, J., (1999) Coord. Chem. Rev., 193-195, pp. 643-690
Delaude, L., Demonceau, A., Wouters, J., (2009) Eur. J. Inorg. Chem., pp. 1882-1891
Kuhn, N., Bohnen, H., Henkel, G., (1994) Z. Naturforsch., B: Anorg. Chem., Org. Chem., 49, pp. 1473-1480
Sereda, O., Blanrue, A., Wilhelm, R., (2009) Chem. Commun., pp. 1040-1042
Kuchenbeiser, G., Soleilhavoup, M., Donnadieu, B., Bertrand, G., (2009) Chem.-Asian. J., 4, pp. 1745-1750
Miguel, D., Riera, V., Miguel, J.A., Bois, C., Philoche-Levisalles, M., Jeannin, Y., (1987) J. Chem. Soc., Dalton Trans., pp. 2875-2880
Alvarez, B., Miguel, D., Pérez-Martínez, J.A., Riera, V., García-Granda, S., (1992) J. Organomet. Chem., 427, pp. C33-C36
Allen, F.H., Watson, D.G., Brammer, L., Orpen, A.G., Taylor, R., (2006) International Tables for Crystallography, 100, pp. 790-811. , ed. E. Prince, Springer, Berlin
Stone, N.J., (2014) Table of nuclear magnetic dipole and electric quadrupole moments, INDC(NDS)-0658, , IAEA, Vienna
Carriedo, G.A., Riera, V., (1981) J. Organomet. Chem., 205, pp. 371-379