This paper reports on the synthesis, X-ray structure, magnetic properties, and DFT calculations of [{HC(CMeNAr)(2)}Mn](2) (Ar = 2,6-iPr(2)C(6)H(3)) (2), the first complex with three-coordinate manganese(l). Reduction of the iodide [{HC(CMeNAr)(2)}Mn(mu-l)](2) (1) with Na/K in toluene afforded 2 as dark-red crystals. The molecule of 2 contains a Mn-2(2+) core with a Mn-Mn bond. The magnetic investigations show a rare example of a high-spin manganese(l) complex with an antiferromagnetic interaction between the two Mn(l) centers. The DFT calculations indicate a strong s-s interaction of the two Mn(l) ions with the open shell configuration (3d(5)4s(1)). This suggests that the magnetic behavior of 2 could be correctly described as the coupling between two S-1 = S-2 = (5)/(2) spin centers. The Mn-Mn bond energy is estimated at 44 kcal mol(-1) by first principle calculations with the B3LYP functional. The further oxidative reaction of 2 with KMnO4 or 02 resulted in the formation of manganese(III) oxide [{HC(CMeNAr)(2)}Mn(mu-O)](2) (3). Compound 3 shows an antiferromagnetic coupling between the two oxo-bridged manganese(III) centers by magnetic measurements.

Synthesis and Reaction of [{HC(CMeNAr)2}Mn]2 (Ar = 2,6-iPr2C6H3): the Complex Containing Three-coordinate Manganese(I) with a Mn-Mn Bond Exhibiting Unusual Magnetic Properties and Electronic Structure / Chai, J.; Zhu, H.; Stckl, A. C.; Roesky, HERBERT W.; Magull, J.; Bencini, Alessandro; Caneschi, Andrea; Gatteschi, Dante. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - STAMPA. - 127:(2005), pp. 9201-9206. [10.1021/ja042269e]

Synthesis and Reaction of [{HC(CMeNAr)2}Mn]2 (Ar = 2,6-iPr2C6H3): the Complex Containing Three-coordinate Manganese(I) with a Mn-Mn Bond Exhibiting Unusual Magnetic Properties and Electronic Structure

BENCINI, ALESSANDRO;CANESCHI, ANDREA;GATTESCHI, DANTE
2005

Abstract

This paper reports on the synthesis, X-ray structure, magnetic properties, and DFT calculations of [{HC(CMeNAr)(2)}Mn](2) (Ar = 2,6-iPr(2)C(6)H(3)) (2), the first complex with three-coordinate manganese(l). Reduction of the iodide [{HC(CMeNAr)(2)}Mn(mu-l)](2) (1) with Na/K in toluene afforded 2 as dark-red crystals. The molecule of 2 contains a Mn-2(2+) core with a Mn-Mn bond. The magnetic investigations show a rare example of a high-spin manganese(l) complex with an antiferromagnetic interaction between the two Mn(l) centers. The DFT calculations indicate a strong s-s interaction of the two Mn(l) ions with the open shell configuration (3d(5)4s(1)). This suggests that the magnetic behavior of 2 could be correctly described as the coupling between two S-1 = S-2 = (5)/(2) spin centers. The Mn-Mn bond energy is estimated at 44 kcal mol(-1) by first principle calculations with the B3LYP functional. The further oxidative reaction of 2 with KMnO4 or 02 resulted in the formation of manganese(III) oxide [{HC(CMeNAr)(2)}Mn(mu-O)](2) (3). Compound 3 shows an antiferromagnetic coupling between the two oxo-bridged manganese(III) centers by magnetic measurements.
2005
127
9201
9206
Chai, J.; Zhu, H.; Stckl, A. C.; Roesky, HERBERT W.; Magull, J.; Bencini, Alessandro; Caneschi, Andrea; Gatteschi, Dante
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Utilizza questo identificatore per citare o creare un link a questa risorsa: https://hdl.handle.net/2158/205009
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