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Towards the Synthesis of Guanidinate- and Amidinate-Bridged Dimers of Mn and Ni
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Applied Physical Chemistry.
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2014 (English)In: Australian journal of chemistry (Print), ISSN 0004-9425, E-ISSN 1445-0038, Vol. 67, no 7, 1081-1087 p.Article in journal (Refereed) Published
Abstract [en]

Reactions of Cp2M (Cp = cyclopentadienyl, M = Mn, Ni) with lithium amidinates and guanidinates are reported. The highly oxophilic nature of Mn leads to the isolation of the interstitial oxide Mn4O(MeN - CH - NMe)(6) (4) in preference to the intended paddle-wheel homodimer Mn-2(MeN - CH - NMe)(4) when employing the sterically uncongested amidinate [MeN - CH - NMe](-) ligand. In contrast, an analogous reaction using Cp2Ni yielded Ni-2(MeN - CH - NMe)(4) (5). The use of monoprotic guanidinate ligands also gave contrasting results for Mn and Ni. In the first case, the highly unusual spirocycle Mn{mu-NC(NMe2)(2)}(4)Li-2 center dot 3THF (6) was produced in low yield. For M = Ni, use of the [hpp](-) (1,3,4,6,7,8hexahydro-2H-pyrimido[1,2-alpha] pyrimidinate) ligand gives results comparable with the synthesis of 5, with Ni-2(hpp) 4 (7) isolated. In contrast to recent data obtained using Cp2Cr, the guanidinate ligands do not sequester coformed CpLi. Density functional theory analysis corroborates the view that the intermetal distance in each of the reported dinickel paddle-wheel complexes (2.4846(8) and 2.3753(5) angstrom in 5 and 7 respectively) is defined by the geometric parameters of the bidentate ligands and that intermetal bonding is not present.

Place, publisher, year, edition, pages
2014. Vol. 67, no 7, 1081-1087 p.
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URN: urn:nbn:se:kth:diva-150942DOI: 10.1071/CH14271ISI: 000340281100017ScopusID: 2-s2.0-84904425887OAI: diva2:745954

QC 20140911

Available from: 2014-09-11 Created: 2014-09-11 Last updated: 2014-09-11Bibliographically approved

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