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Synthesis and coordination properties of new σ23-P/N switchable chelators based on [1,2,3]-diazaphosphole

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Abstract

Novel hybrid ligands based on [1,2,3]-diazaphosphole (dap) were prepared and their coordination behaviour toward selected transition metals has been studied. The syntheses and spectroscopic properties of polydentate bis(5-t-butyl-[1,2,3]-diazaphosphol-2-yl)-dimethylsilane (BdapsH,tBu) and bis(4-methyl-5-ethyl-[1,2,3]-diazaphosphol-2-yl)-dimethylsilane (BdapsMe,Et) are reported. In zerovalent compounds of the type [M(CO)42-P,P′-BdapsR1,R2)] (R1 = Me, R2 = Et, M = Cr, Mo and W; R1 = H, R2 = t-Bu, M = W) and [Ni(κ2-P,P′-BdapsH,tBu)2] the ligand serves as a P,P′-donor, giving rigid six-membered chelate rings. BdapsMe,Et is also capable of behaving as an N,N′-chelator as confirmed by isolation of high-spin chelate complex [CoBr22-N,N′-BdapsMe,Et)]. The reaction of parent 2H-4-methyl-5-ethyl-[1,2,3]-diazaphosphole with NiBr2·DME yielded paramagnetic compound [NiBr2(κ-N-dap)2], where the dap heterocycle bonds with the nickel(II) centre via a 1-nitrogen donor atom in a distorted tetrahedral environment. All the studied complexes showing different coordination modes of the new ligands were fully characterized, including single-crystal X-ray diffraction analysis.

Graphical abstract: Synthesis and coordination properties of new σ2,λ3-P/N switchable chelators based on [1,2,3]-diazaphosphole

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Publication details

The article was received on 17 Jun 2019, accepted on 22 Jul 2019 and first published on 23 Jul 2019


Article type: Paper
DOI: 10.1039/C9NJ03146D
New J. Chem., 2019, Advance Article

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    Synthesis and coordination properties of new σ23-P/N switchable chelators based on [1,2,3]-diazaphosphole

    P. Kozáček, L. Dostál, A. Růžička, I. Císařová, Z. Černošek and M. Erben, New J. Chem., 2019, Advance Article , DOI: 10.1039/C9NJ03146D

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