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Journal ArticleDOI

Main group complexes incorporating 1,3-bis(furyl)-1,1,3,3-tetramethyldisilazide ligands

15 May 2007-Journal of Organometallic Chemistry (Elsevier)-Vol. 692, Iss: 12, pp 2548-2553
TL;DR: In this article, the lithium salt of the bis-furyl substituted disilazide anion, Li{i] [{i} = N(SiMe2R)2 where R = 2-methylfuryl] has been examined as a ligand transfer reagent for the synthesis of group 2 (magnesium) and group 13 (aluminium) compounds.
About: This article is published in Journal of Organometallic Chemistry.The article was published on 2007-05-15. It has received 6 citations till now. The article focuses on the topics: Homoleptic & Amide.
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Journal ArticleDOI
TL;DR: The simultaneous presence of methyl groups at the C(2) and N(1) atoms of 2-acetylthiophene-N(1)-methylthiosemicarbazone (HattscN-Me) have facilitated the binding of triphenylphosphine in three-coordinate copper(i) halide complexes, which represent an unusual donor set of ligands, namely, triphensylph phosphine, sulfur of a thio-ligand and
Abstract: The influence of substituents at the C2carbon of N1-substituted thiosemicarbazones, {C4H3X–C2(CH3)N3–N2H–C1(S)N1HR2} (X = O, S) on the geometry of nickel(II) complexes has been investigated. The presence of a methyl group at the C2 position of 2-acetylfuran-N1-substituted thiosemicarbazones {(C4H3O)–C2(CH3)N3–N2H–C1(S)N1HR2, R2 = CH3, HaftscN–Me; C2H5, HaftscN–Et; C6H5, HaftscN–Ph} induces unusual coordination by the furan ring and yielded high spin octahedral nickel(II) complexes, [Ni(κ3-O, N3, S-aftscN–R2)2], CH31, C2H52, and 2[Ni((κ3-O, N3, S-aftscN–Ph)2] 3 (μeff = 2.98, 1; 2.96, 2; 2.92, 3). With 2-acetylthiophene-N1-substituted thiosemicarbazones, {(C4H3S)-C2(CH3)N3-N2H–C1(S)N1HR2, R2 = CH3, HattscN–Me; C2H5, HattscN–Et; C6H5, HattscN–Ph}, N3, S chelated low spin trans square planar complexes, {[Ni(κ3-O, N3, S-attscN–R2)2], R2 = CH3, 4; C2H5, 5; C6H5, 6} with pendant thiophene rings have been obtained. The bigger sized sulfur atoms of the thiophene rings form short intramolecular contacts with the deprotonated hydrazinic nitrogen atoms (S⋯N2) inhibiting its lability for possible coordination to nickel(II). Complexes have one independent molecule (1) or two independent molecules (2, 3) in their respective crystal lattices. The simultaneous presence of methyl groups at the C2 and N1 atoms of 2-acetylthiophene-N1-methylthiosemicarbazone (HattscN–Me) have facilitated the binding of triphenylphosphine in three-coordinate copper(I) halide complexes, [CuX(η1-S-HattscN–Me)(Ph3P)] (X, Br, 7; Cl, 8), which represent an unusual donor set of ligands, namely, triphenylphosphine, sulfur of a thio-ligand and a halide.

44 citations

Journal ArticleDOI
TL;DR: This study provides new insights into the ability of this bimetallic base to facilitate direct Mg-H exchange reactions as well as to exhibit polybasicity and heteroleptic tris(amido)magnesiates.
Abstract: Exploring the reactivity of sodium butylmagnesiate reagent [{Na(THF)6}+{(Ph2Si(NAr*)2)Mg(Bu)(THF)}−] (1) supported by the bulky chelating silyl(bisamido) ligand {Ph2Si(NAr*)2}2− (Ar* = 2,6-iPr2-C6H3) towards N-methylbenzimidazole (bImMe), pyrrole and 2,6-diisopropylaniline (NH2Ar*), this study provides new insights into the ability of this bimetallic base to facilitate direct Mg–H exchange reactions as well as to exhibit polybasicity. Thus 1 effectively promotes the deprotomagnesiation of bImMe under mild reaction conditions to give the α-metallated intermediate [{Na(THF)5}2+{(Ph2Si(NAr*)2)Mg(bImMe*)}2−] (2) (bImMe* = 2-N-methylbenzimidazolyl). Analysis of crystallographic and NMR data of 2 combined with DFT calculations show that the metallated C in the bImMe* ligands possesses a significant carbenic character. Contrasting with previous studies of benzothiazole (btz), 1 does not react with an excess of bImMe even under forcing refluxing conditions. Contrastingly, the amination reactions of equimolar amounts of 1 with pyrrole and 2,6-diisopropylaniline allowed the isolation of [{(Ph2Si(NAr*)(NHAr*))Mg(NC4H4)2(THF)Na(THF)2}] (3) and [{Na(THF)6}+{(Ph2Si(NAr*)(NHAr*))Mg(NHAr*)2(THF)}−] (4) respectively as crystalline solids. Highlighting the ability of 1 to act as a polybasic reagent, 3 and 4 are formed as the result of the deprotonation of two molecules of the relevant amine via its butyl group and one amido arm of the silyl(bisamido) ligand. Similarly, the reactions of 1 with 3 molar equivalents of the relevant amine yielded homoleptic tris(amido) compounds [(THF)2NaMg(NC4H4)3] (5) and [{Na(THF)6}+{Mg(NHAr*)3}−] (7), with the concomitant formation of bis(amine) Ph2Si(NHAr)2, as a result of the complete amination of 1 using its three basic sites. The structures in the solid state of 3 and 4 were elucidated by X-ray crystallography. Despite their similar constitution, these heteroleptic tris(amido)magnesiates adopt contrasting structures, with the former displaying a contacted ion-pair structure, where Na and Mg are connected by two bridging pyrrolyl anions, whereas the latter gives rise to a solvent-separated ion pair motif. To the best of our knowledge 3 represents the first crystallographically characterized magnesium compound containing an anionic non-substituted form of pyrrole. Noticeably, Mg interacts exclusively with the N atoms of the pyrrolyl ligands, forming strong σ-bonds, whereas Na prefers to engage with the π-systems of both NC4-rings.

15 citations

Journal ArticleDOI
TL;DR: A series of mono-and bis-amide scandium and yttrium compounds incorporating the furyl-substituted disilazide ligand, [N{SiMe2R}2] {i} (where R = 2-methylfuryl) have been synthesized as mentioned in this paper.

10 citations

Journal ArticleDOI
17 Jul 2007
TL;DR: In this article, the authors reflect major advances in the coordination and organometallic chemistry of the alkali and alkaline earth elements that appeared in peer-reviewed journals throughout 2007.
Abstract: The aim of this chapter is to reflect major advances in the coordination and organometallic chemistry of the alkali and alkaline earth elements that appeared in peer-reviewed journals throughout 2007. These self-imposed limitations necessarily result in the omission of a great number of noteworthy advances in related fields rooted in either solid-state, materials or theoretical chemistry. The author apologises in advance, therefore, that not all published work can be afforded the same depth of coverage.

9 citations

Journal ArticleDOI
TL;DR: The catalytic activity of selected complexes in the polymerization of ethylene is reported, and the molecular structures of 1a, 1b, [3a]2, 4b, 5b and 6b have been solved using single-crystal X-ray diffraction techniques, indicating varying nuclearity of the complexes and hapticities for the amide ligands in the solid-state.
Abstract: The stoichiometric reaction between the previously described lithium amide salts, LiN(SiMe2R)2 [Li{i}, R = furyl, Li{ii}, R = 2-methylfuryl] and titanium(IV)chloride at low temperature afforded the mono-amide compounds Ti{i}Cl3 (1a) and Ti{ii}Cl3 (1b). The analogous zirconium derivatives Zr{i}Cl3 (3a) and Zr{ii}Cl3 (3b) were accessed via the reaction of excess trimethylsilylchloride with the mixed tetra-amide species, Zr{i}(NMe2)3 (2a) and Zr{ii}(NMe2)3 (2b). The bis-amide complexes Ti{ii}2Cl2 (4b), Zr{i}2Cl2 (5a) and Zr{ii}2Cl2 (5b) were synthesized in a straightforward salt metathesis reaction employing two equivalents of Li{i} or Li{ii} with the metal salts, MCl4(THF)2. The reactivity of the halide compounds 1 and 3–5 with a variety of alkylating agents was studied, with ligand transfer from the transition-element to the main group metal-alkyl reagent being the predominant reaction pathway. The reaction of 4b with MeLi was, however, partially successful affording the titanium(III) complex, Ti{ii}2X (X = Cl/Me, 6b′); this compound was subsequently made as the pure chloride 6b from the reaction of two equivalents of Li{ii} with TiCl3(THF)3. The targeted dialkyl species, Ti{ii}Me2 (7b), was successfully isolated from the reaction between the dichloride 4b and dimethylmagnesium. The molecular structures of 1a, 1b, [3a]2 [3b]2, 4b, 5b and 6b have been solved using single-crystal X-ray diffraction techniques, indicating varying nuclearity of the complexes and hapticities for the amide ligands in the solid-state. The catalytic activity of selected complexes in the polymerization of ethylene is reported.

8 citations

References
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Journal ArticleDOI
TL;DR: In this article, the linear quadridentate N2S2 donor ligand 1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane (bmdhp) forms mono-and di-hydrate 1 : 1 copper(II) complexes which are significantly more stable toward autoreduction than those of the non-methylated analogue.
Abstract: The linear quadridentate N2S2 donor ligand 1,7-bis(N-methylbenzimidazol-2′-yl)-2,6-dithiaheptane (bmdhp) forms mono- and di-hydrate 1 : 1 copper(II) complexes which are significantly more stable toward autoreduction than those of the non-methylated analogue. The deep green monohydrate of the perchlorate salt crystallises as the mononuclear aqua-complex, [Cu(bmdhp)(OH2)][ClO4]2, in the monoclinic space group P21/n, with Z= 4, a= 18.459(3), b= 10.362(2), c= 16.365(3)A, and β= 117.14(1)°. The structure was solved and refined by standard Patterson, Fourier, and least-squares techniques to R= 0.047 and R′= 0.075 for 3 343 independent reflections with l > 2σ(l). The compound consists of [Cu(bmdhp)(OH2)]2+ ions and ClO4– counter ions. The co-ordination around copper is intermediate between trigonal bipyramidal and square pyramidal, with Cu–N distances of 1.950(4) and 1.997(4)A, Cu–O(water) 2.225(4)A, and Cu–S 2.328(1) and 2.337(1)A. In the solid state, the perchlorate dihydrate's co-ordination sphere may be a topoisomer of the monohydrate's. A new angular structural parameter, τ, is defined and proposed as an index of trigonality, as a general descriptor of five-co-ordinate centric molecules. By this criterion, the irregular co-ordination geometry of [Cu(bmdhp)(OH2)]2+ in the solid state is described as being 48% along the pathway of distortion from square pyramidal toward trigonal bipyramidal. In the electronic spectrum of the complex, assignment is made of the S(thioether)→ Cu charge-transfer bands by comparison with those of the colourless complex Zn(bmdhp)(OH)(ClO4). E.s.r. and ligand-field spectra show that the copper(II) compounds adopt a tetragonal structure in donor solvents.

7,886 citations

Journal ArticleDOI
TL;DR: FeFeCl3 and CoCl2 reagieren mit NaN[Si(CH3)3]2 zu grun gefarbten, sublimierbaren bzw. destillierberen Disilylmetallamiden der Zusammensetzung Fe
Abstract: FeCl3 und CoCl2 reagieren mit NaN[Si(CH3)3]2 zu grun gefarbten, sublimierbaren bzw. destillierbaren monomeren Disilylmetallamiden der Zusammensetzung Fe{N[Si(CH3)3]2}3 (I) und Co{N[Si(CH3)3]2}2 (II). Die Verbindungen losen sich leicht in organischen Losungsmitteln und addieren keine weiteren Liganden.

135 citations

Journal ArticleDOI
TL;DR: An overview of the strategy used to come up with the design of a new type of ligand that is appropriate for coordination to both the late metals and the early metals is given in this paper.
Abstract: An overview is given on the strategy used to come up with the design of a new type of ligand that is appropriate for coordination to both the late metals and the early metals. The coordination chem...

97 citations

Journal ArticleDOI
TL;DR: In this article, the authors reagiert with CrCl3, MnJ2, NiJ2 and CuJ in Tetrahydrofuran zu fluchtigen, sehr hydrolyse-und sauerstoffempfindlichen Disilylamiden des Cr(III), Mn(II), Ni(II) and Cu(I).
Abstract: Natrium-bis-(trimethylsilyl)-amid reagiert mit CrCl3, MnJ2, NiJ2 und CuJ in Tetrahydrofuran zu fluchtigen, sehr hydrolyse-und sauerstoffempfindlichen Disilylamiden des Cr(III), Mn(II), Ni(II) und Cu(I).

94 citations

Journal ArticleDOI
TL;DR: In this article, the reactivite de complexes avec des derives du phosphore is discussed, in the context of synthetique de travaux, bibliographiques, etc.

85 citations

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