An Organocadmium Hydroxylamide Surajit Jana, †,‡ Roland Fröhlich, § Alexander Hepp, † and Norbert W. Mitzel* ,‡,| NRW Graduate School of Chemistry, Institut für Anorganische and Analytische Chemie, and Organisch-chemisches Institut, UniVersity of Münster, Münster, Germany, and Fakultät für Chemie, UniVersität Bielefeld, UniVersitätsstrasse 25, 33615 Bielefeld, Germany ReceiVed December 10, 2007 Summary: The first organometallic cadmium hydroxylamide [Cd(MeCd) 4 (ONEt 2 ) 6 ](1) has been prepared by alkane elimina- tion from dimethylcadmium upon treatment with N,N-diethyl- hydroxylamine and characterized by Variable-temperature NMR spectroscopy ( 1 H, 13 C, 113 Cd), single-crystal X-ray diffraction, and elemental analysis. In the solid state compound 1 comprises an Cd 5 N 6 O 6 backbone with a central octahedral coordinate Cd atom, while all 12 donor atoms are attached to the 5 Cd nuclei whereas in solution it is of highly dynamic nature. Introduction The chemistry of the hydroxylamides of the trivalent group 13 elements with their different structural motifs is well established. 1 The high coordination flexibility of the hydroxy- lamide ligands has been demonstrated in Al and Ga organo- metallics (e.g., in the readily fluctuating tetracyclic trinuclear Al 3 aggregate [{(Me 2 Al)[ONMe] 2 CH 2 } 2 (AlMe)] 2 ). It can be expected that this allows for the construction of highly dynamic Zn or Cd based multinuclear aggregates. This is because compared with trivalent group 13 elements, group 12 atoms require further contacts to a donor atom to achieve coordination number four due to their divalent nature. Hydroxylamine derivatives of the elements Zn and Cd were unknown, except the neutral hydroxylamine complex (H 2 NOH) 2 ZnCl 2 (Chris- mer’s salt), 3 until recently some of us reported on hydroxylamide complexes of zinc, 4 which show highly dynamic behavior in solution. We have also succeeded in the preparation of the first mixed hydroxylamide-hydrazide aggregates of zinc of the type [Zn(RZn) 4 (NHNR′ 2 ) 2 (ONEt 2 ) 4 ]. 5 However, up to now no cad- mium hydroxylamine compounds are known, despite cadmium having a rich alkoxide chemistry. 6 Such an organocadmium aggregate compound with hydroxylamide substituents is reported in this contribution. Results and Discussions The reaction of dimethylcadmium with N,N-diethylhydroxy- lamine in an equimolar ratio leads to the formation of the cadmium hydroxylamide complex [Cd(MeCd) 4 (ONEt 2 ) 6 ](1) (Scheme 1), the first hydroxylamide of cadmium. Compound 1 is sparingly soluble in pentane and hexane, but well soluble in toluene and ethereal solvents. The compound was characterized by NMR spectroscopy, elemental analysis, and also X-ray crystal structure determination. Single crystals of 1 were obtained from a solvent mixture of n-hexane/toluene (2:1) upon prolonged times of keeping con- centrated solutions at –26 °C. Compound 1 crystallizes in the triclinic system, space group P1 j . Toluene molecules fill the voids in the crystal structure, but have no significant contacts with any of the atoms of 1. Figure 1 depicts the molecular structure of 1. The central Cd atom of the hydroxylamide aggregate [Cd(MeCd) 4 (ONEt 2 ) 6 ](1) adopts an octahedral coordination sphere by binding to the O atoms of all six O-N ligands. Formally an anionic fragment [Cd(ONEt 2 ) 6 ] 4- can be assigned to constitute the center. The charge of this is compensated by four formally cationic MeCd + groups. As all O and N atoms are coordinated to Cd atoms, two possible modes of connectivity with the MeCd fragments are observed: N,O,O or N,N,O. Consequently, aggregate 1 is one of the limited examples of Cd species that exhibit mixed coordination numbers. 7 A similar structural type of aggregation was recently reported for an analogous zinc compound * Corresponding author. E-mail: mitzel@uni-bielefeld.de. † Institut für Anorganische and Analytische Chemie, Universität Münster, Corrensstrasse 30, D-48149 Münster. ‡ NRW Graduate School of Chemistry, Universität Münster, Correns- strasse 30, D-48149 Münster. § Organisch-chemisches Institut, Universität Münster, Corrensstrasse 40, D-48149 Münster. | Fakultät für Chemie, Universität Bielefeld, Universitätsstrasse 25, D-33615 Bielefeld. (1) (a) Hausen, H. D.; Schmöger, G.; Schwarz, W. J. Organomet. Chem. 1978, 153, 271. (b) Mitzel, N. W.; Lustig, C.; Woski, M. Dalton Trans. 2004, 397. (2) (a) Mitzel, N. W.; Lustig, C. Angew. Chem. 2001, 113, 4521. (b) Angew. Chem., Int. Ed. 2001, 40, 4390. (3) (a) Chrismer, A. Bull. Soc. Chim. 1890, 3, 119. (b) Walker, J. E.; Howell, D. M. Inorg. Synth. 1967, 9, 2 and references cited therein. (4) Ullrich, M.; Berger, R. J. F.; Lustig, C.; Fröhlich, R.; Mitzel, N. W. Eur. J. Inorg. Chem. 2006, 4219. (5) Jana, S.; Berger, R. J. F.; Fröhlich, R.; Mitzel, N. W. Chem. Commun. 2006, 3993. (6) (a) Coates, G. E.; Lauder, A. J. Chem. Soc. 1966, A264. (b) Maciel, G. E.; Borzo, M. J. Chem. Soc., Chem. Commun. 1973, 394. (c) Maciel, G. E. NMR Spectroscopy of nuclei other than protons; Axenrod, T., Webb, G. A., Eds.; Wiley: New York, 1974; p 347. (d) Holmes, J. R.; Kaesz, H. D. J. Am. Chem. Soc. 1961, 83, 3903. (e) Nöth, H.; Thomann, M. Chem. Ber. 1995, 128, 923. (f) Ramsey, N. F. Phys. ReV. 1950, 78, 699. (g) Jana, S.; Pape, T.; Mitzel, N. W. Z. Naturforsch., B: Chem. Sci. 2007, 62b, 1339. (7) Boyle, T. J.; Bunge, S. D.; Alam, T. M.; Holland, G. P.; Headley, T. J.; Avilucea, G. Inorg. Chem. 2005, 44, 1309. Scheme 1 Organometallics 2008, 27, 1348–1350 1348 10.1021/om7012343 CCC: $40.75  2008 American Chemical Society Publication on Web 02/28/2008