Abstract
Deliberate hydrolysis of lithium cyclo-propyl-alkynylamidinates, Li[c-C3H5-C≡C(NR')2] [R' = i Pr, Cy = cyclo-hex-yl)], afforded the hitherto unknown neutral cyclo-propyl-alkynyl-amidine derivatives c-C3H5-C≡C-C(NR')(NHR') [R' = i Pr (1), Cy (2)]. Subsequent reactions of 1 or 2 with metal(II) chlorides, MCl2 (M = Mn, Fe, Co), provided the title complexes di-chlorido-bis-(3-cyclo-propyl-N,N'-diisopropyl-prop-2-ynamidine)-manganese(II), [MnCl2(C12H20N2)2], (3), di-chlorido-bis-(3-cyclo-propyl-N,N'-diisopropyl-prop-2-ynamidine)-iron(II), [FeCl2(C12H20N2)2], (4), di-chlorido-bis-(N,N'-di-cyclo-hexyl-3-cyclo-propyl-prop-2-ynamidine)-iron(II), [FeCl2(C18H28N2)2], (5), and di-chlorido-bis-(N,N'-di-cyclo-hexyl-3-cyclo-propyl-prop-2-ynamidine)-cobalt(II), [CoCl2(C18H28N2)2], (6), or more generally MCl2[c-C3H5-C≡C-C(NR')(NHR')]2 [R' = i Pr, M = Mn (3), Fe (4); R' = Cy, M = Fe (5), Co (6)] in moderate yields (30-39%). Besides their spectroscopic data (IR and MS) and elemental analyses, all complexes 3-6 were structurally characterized. The two isopropyl-substituted complexes 3 and 4 are isotypic, and so are the cyclo-hexyl-substituted complexes 5 and 6. In all cases, the central metal atom is coordinated by two Cl atoms and two N atoms in a distorted-tetra-hedral fashion, and the structure is supported by intra-molecular N-H⋯Cl hydrogen bonds.
Highlights
Over the past three decades, chelating anionic 1,3-diazaallyltype ligands such as amidinates, [RC(NR0)2]À, and guanidinates, [R2NC(NR0)2]À, have gained tremendous importance in various fields of organometallic and coordination chemistry
We described the synthesis and characterization of a series of lithium cyclopropylethinylamidinates, Li[c-C3H5—C C—C(NR0)2] [R0 = iPr, Cy (= cyclohexyl)], which are readily accessible on a large scale using commercially available starting materials
We report here the deliberate synthesis of two new cylopropylalkynylamidines, c-C3H5—C C—C(NR0)(NHR0) (R0 = iPr, Cy) as well as the preparation and structural characterization of four first-row transition metal complexes of the type MCl2[c-C3H5—C C— C(NR0)(NHR0)] (M = Mn, Fe, Co; R0 = iPr, Cy)
Summary
Over the past three decades, chelating anionic 1,3-diazaallyltype ligands such as amidinates, [RC(NR0)2]À, and guanidinates, [R2NC(NR0)2]À, have gained tremendous importance in various fields of organometallic and coordination chemistry. We described the synthesis and characterization of a series of lithium cyclopropylethinylamidinates, Li[c-C3H5—C C—C(NR0)2] [R0 = iPr, Cy (= cyclohexyl)], which are readily accessible on a large scale using commercially available starting materials (cyclopropylacetylene, N,N0-diorganocarbodiimides; Sroor et al, 2013) These ligands have been employed for the preparation of new di- and trivalent lanthanide complexes (Sroor et al, 2015a,b,c,d, 2016; Wang et al, 2016). In the course of this work, we occasionally observed and structurally characterized hydrolysis products of the composition MCl2[c-C3H5—C C—C(NR0)(NHR0)] (M = Mn, Fe, Co; R0 = iPr, Cy), which contain the neutral amidines c-C3H5-C C— C(NR0)(NHR0) as new ligands. The hydrogen-bonded NÁ Á ÁCl separations are similar in 3–6, being in the narrow range of 3.175 (3)– 3.251 (2) A (Tables 1–4)
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