Zinc Center Research Articles

Исследование галогенидов натрия и меди методом мессбауэровской спектроскопии на изотопе -=SUP=-67-=/SUP=-Zn

The central shifts of the emission Mössbauer spectra on 67Cu(67Zn) impurity atoms in the crystal lattices of sodium and copper halides are determined, the relativistic Doppler shifts of the spectra are calculated, and, as a result, isomeric shifts are obtained, which are compared with the nature of the chemical bonding of zinc atoms with halogen atoms in the studied crystals. The values of the quadrupole interaction constants for impurity zinc centers in sodium halides are consistent with the results of calculating these values within the framework of the ionic model.

Design and synthesis of a solution-processed redox-active bis(formazanate) zinc complex for resistive switching applications.

In this paper, we report the synthesis and characterization of a mononuclear zinc complex (1) containing a redox-active bis(4-antipyrinyl) derivative of the 3-cyanoformazanate ligand. Complex 1 was readily obtained by refluxing zinc acetate with 3-cyano-1,5-(4-antipyrinyl)formazan (LH) in a methanolic solution. Single-crystal X-ray diffraction analysis of complex 1 shows that the formazanate ligands bind to the zinc center in a five-member chelate "open" form via the 1- and 4-positions of the 1,2,4,5-tetraazapentadienyl formazanate backbone leading to the formation of the mononuclear bis(formazanate) zinc complex exhibiting a distorted octahedral geometry. We also report the study of resistive-switching random access memory application of this solution-processable bis(formazanate) Zn(II) complex to facilitate the practical implementation of transition metal complex-based molecular memory devices. The complex demonstrated high conductance switching with a large ON-OFF ratio, good stability, and a long retention time. A trap-controlled space charge limited current mechanism is proposed for the observed resistive switching behavior of the device, wherein the role played by the [ZnIIL2] complex that comprises the extended redox-active conjugated ligand backbone is revealed by corroborating electrochemical studies, spectrochemical experiments, and DFT calculations. In addition to providing significant insights into the molecular design of transition metal complexes for memory applications, this study also presents the utilization of ZnIIL2 towards the realization of non-volatile resistive random access memory (RRAM) devices with inorganic/organic hybrid active layers that are highly cost-effective and sustainable. These devices exhibited multilevel switching and low current operation, both of which are desirable for advanced memory applications.

Covalently linked pyrene antennas for optically dense yet aggregation-resistant light-harvesting systems.

In this study we present a novel energy transfer material inspired by natural light-harvesting antenna arrays, zinc(II) phthalocyanine-pyrene (ZnPcPy). The ZnPcPy system facilitates energy transfer from 16 covalently linked pyrene (Py) donor chromophores to the emissive central zinc(II) phthalocyanine (ZnPc) core. Nearly 98% energy transfer efficiency is determined from the changes in emission decay rates between free MePy to covalently linked Py, supported by comparisons of photoluminescence quantum yields using different excitation wavelengths. A comparative analysis of ZnPcPy and an equivalent mixture of ZnPc and MePy demonstrates the superior light-harvesting performance of the covalently linked system, with energy transfer rates 9705 times higher in the covalently bound system. This covalent strategy allows for very high loadings of absorbing Py chromophores to be achieved while also avoiding exciton quenching that would otherwise arise, with the same strategy widely applicable to other pairs of Főrster resonance energy transfer (FRET) chromophores.

Synthesis, Spectral Studies and Antimicrobial Activity of Zinc(II) Azide Complexes with N,N-Donor and N,N,S-Donor Schiff Base Ligands Derived from 2-Pyridinecarboxaldehyde

Two water soluble Zn(II) Schiff base complexes of composition [Zn(L1)3][Zn(N3)4] (1) and [Zn(L2)2][Zn(N3)4] (2) were synthesized using bidentate N,N-donor (L1) and tridentate N,N,S-donor (L2) of Schiff base ligands viz. (E)-1-phenyl-N-(pyridin-2-ylmethylene)methanamine (L1) and (E)-2-((pyridin-2-ylmethylene)amino)benzenethiol (L2). Different spectroscopic tools such as FT-IR, UV-Vis, 1H NMR and fluorescence spectroscopy have been employed to characterize complexes 1 and 2. Efforts for getting single crystals suitable for X-ray crystal structure could not be achieved. However, from the spectroscopic data and on the basis of the structures of the related zinc(II) complexes reported earlier in the literature, the complexes could be proposed to adopt six coordinated octahedral geometries in one zinc centre coordinated to the ligands and while the other zinc centre has four azides (N3) terminally coordinated resulting in the octahedral and tetrahedral metal geometries around zinc metal atoms. The compounds behave as electrolytes in acetonitrile solution. In vitro antimicrobial activity of the Zn(II) complexes were studied against some microbes like Aspergillus niger, Fusarium ventricossum and Fusarium chlamydosporum. Effective antifungal activity of complex 2 was found against the tested fungal strains.

Synthesis, Crystal Structure, and Optical Properties of a Trinuclear Zinc(II) Complex with Rhodamine B

A heteroleptic homotrinuclear complex, [Zn3(valhydr)2(RhB)2(EtOH)2](ClO4)2 (H2valhydr = 1,2-bis(2-hydroxy-3-methoxybenzylidene)hydrazine, RhB = rhodamine B), was synthesized and structurally characterized by X-ray diffraction on single crystal. In the centrosymmetric complex, the zinc ions are positioned in a linear manner. The external zinc ions are pentacoordinated with a distorted square pyramidal stereochemistry, while the central zinc ion presents an elongated octahedral geometry. Luminescent properties of the complex were investigated in solid state and solution.

Heteroligand α-Diimine-Zn(II) Complexes with O,N,O′- and O,N,S-Donor Redox-Active Schiff Bases: Synthesis, Structure and Electrochemical Properties

A number of novel heteroligand Zn(II) complexes (1-8) of the general type (Ln)Zn(NN) containing O,N,O'-, O,N,S-donor redox-active Schiff bases and neutral N,N'-chelating ligands (NN) were synthesized. The target Schiff bases LnH2 were obtained as a result of the condensation of 3,5-di-tert-butyl-2-hydroxybenzaldehyde with substituted o-aminophenols or o-aminothiophenol. These ligands with combination with 2,2'-bipyridine, 1,10-phenanthroline, and neocuproine are able to form stable complexes upon coordination with zinc(II) ion. The molecular structures of complexes 4∙H2O, 6, and 8 in crystal state were determined by means of single-crystal X-ray analysis. In the prepared complexes, the redox-active Schiff bases are in the form of doubly deprotonated dianions and act as chelating tridentate ligands. Complexes 6 and 8 possess a strongly distorted pentacoordinate geometry while 4∙H2O is hexacoordinate and contains water molecule coordinated to the central zinc atom. The electrochemical properties of zinc(II) complexes were studied by the cyclic voltammetry. For the studied complexes, O,N,O'- or O,N,S-donor Schiff base ligands are predominantly involved in electrochemical transformations in the anodic region, while the N,N'-coordinated neutral nitrogen donor ligands demonstrate the electrochemical activity in the cathode potential range. A feature of complexes 5 and 8 with sterically hindered tert-butyl groups is the possibility of the formation of relatively stable monocation and monoanion forms under electrochemical conditions. The values of the energy gap between the boundary redox orbitals were determined by electrochemical and spectral methods. The parameters obtained in the first case vary from 1.97 to 2.42 eV, while the optical bang gap reaches 2.87 eV.

Homo- and heteroleptic 3-methylbenzoates of zinc(II) ion based on N-donor heterocycles; structure, DNA binding and pharmacological evaluation

Herein, one homoleptic (C1) and three heteroleptic zinc(II) carboxylates (C2-C4) were synthesized by using 3-methylbenzoic acid (HL) as primary ligand and N- donor heterocycles, i.e., 2,2′-bipyridine (C2), 1,10-phenanthroline (C3) and 2,9-dimethyl-1,10-phenanthroline (C4) as hetero-ligands. The complexes were characterized by multiple techniques that include (1H and 13C) nuclear magnetic resonance (NMR), Fourier Transform infrared (FTIR) spectroscopy and single crystal X-ray diffraction (XRD) analysis. The FTIR spectra of complexes suggested different coordination modes of the carboxylate ligand around the metal center. The single crystal XRD analysis confirmed dinuclear (C2 and C3) complexes having five coordinated zinc centers with distorted square pyramidal geometry, whereas in the mononuclear complex C4, the tetra-coordinated zinc(II) has a distorted tetrahedral geometry that can also be regarded as five coordinated if the bonding of oxygen (O4) lying at the margined distance of Zn-O bond is to be considered. The SS-DNA interaction study has shown enhanced DNA binding affinity for the heteroleptic complexes C2-C4 compared to the free ligand acid HL and homoleptic complex C1. The in vitro antibacterial and antifungal study validated the chelation theory and overtone’s concept. The enzyme inhibition study data revealed a concentration dependent inhibition of the alkaline phosphatase by the synthesized complexes.

Molecular architecture, characterization, and applications of homoleptic heteronuclear 3d/4f metals’ complexes derived from bi-compartmental Schiff-base

A series of homoleptic heterotrinuclear 3d/4f metal complexes (2-6) of general formula [Zn2Ln(salopn)2(NO3)3H2O].CH3CN.H2O; where Ln = La (2), Nd (3), Sm (4), Gd (5) and Dy (6); have been synthesized by using tetradentate bi-compartmental Schiff base ligand, [2-((E)-(2-((E)-2-hydroxybenzylideneamino)phenylimino)methyl)phenol], and Zn(salopn) precursor (1). The unequivocal evidence of their structural motifs is obtained by characterizing the compounds through FT-IR spectroscopic, and single crystal XRD data, besides the elemental analyses. The trinuclear complex 6 shows that the ligand attached to the metals’ centers, Zn(II) and Dy(III) through N, O and O, O sites respectively. The zinc center is pentacoordinated having distorted square pyramidal geometry and to which Zn-O and Zn-N bond lengths lie in range 2.006-2.035 Å and 2.044-2.060 Å respectively. The dysprosium center is octa-coordinated which is attached to four oxygen atoms from salopn−2 and four oxygens from bidentate nitrate moieties, where Dy-O bond length is in range 2.292-2.517 Å. The photoluminescence (PL) data described that the heteronuclear complexes show characteristic luminescence properties and sensitization across the bi-compartmental ligand. The magnetic parameters for (2-6) are determined and their room temperature χm T and µeff values are found in range 0.18-15.12 emu.mole−1.K and 1.20-10.96 µB respectively that describe the paramagnetic nature.

Fluorescence lifetime imaging of water-soluble porphyrin in human nasopharyngeal cells under two-photon excitation

A comparative study of the two-photon absorption and emission properties of two free-based porphyrins (H2TMPyP and H2TPPS) and their zinc(II) complexes (ZnTMPyP and ZnTPPS) in three polar solvents has been carried out. The presence of the central zinc(II) ion leads to smaller two-photon absorption cross sections (δTPA), while the introduction of methylpyridinium substituents (N•+–CH3) results in larger ones. The δTPA values of H2TMPyP and ZnTMPyP are affected by both the solvent polarity and the hydrogen bonding between porphyrin and solvent molecules. In this work, the strongest two-photon fluorescence is given by H2TMPyP, which may efficiently get into four kinds of nasopharyngeal cell lines (NP69, SUNE1, CNE2, and CNE1) and prefer to localize in the nucleus. Two-photon fluorescence lifetime images of all the cell lines treated with H2TMPyP consist of a short- (τ1) and a long-lived component (τ2). The τ2 distribution of normal cell line NP69 shows one peak lifetime (∼2.12 ns), while those of the cancerous cell lines (SUNE1, CNE2, and CNE1) have two peak lifetimes (∼2.14 and ∼3.77 ns). The τ1 distribution around 0.68 ns is higher for the well differentiated nasopharyngeal cancerous cell line CNE1 compared with the poorly differentiated ones (SUNE1 and CNE2).

Selective area heteroepitaxy of InAs nanostructures on nanopillar-patterned GaAs(111)A

A process sequence enabling the large-area fabrication of nanopillar-patterned semiconductor templates for selective-area heteroepitaxy is developed. Herein, the nanopillar tops surrounded by a SiNx mask film serve as nanoscale growth areas. The molecular beam epitaxial growth of InAs on such patterned GaAs(111)A templates is investigated by means of electron microscopy. It is found that defect-free nanoscale InAs islands grow selectively on the nanopillar tops at a substrate temperature of 425 °C. High-angle annular dark-field scanning transmission electron microscopy imaging reveals that for a growth temperature of 400 °C, the InAs islands show a tendency to form wurtzite phase arms extending along the lateral ⟨112¯⟩ directions from the central zinc blende region of the islands. This is ascribed to a temporary self-catalyzed vapor–liquid–solid growth on {111¯} B facets, which leads to a kinetically induced preference for the nucleation of the wurtzite phase driven by the local, instantaneous V/III ratio, and to a concomitant reduction of surface energy of the nanoscale diameter arms.

Sulfane Decreases the Nucleophilic Reactivity of Zinc Thiolates: Implications for Biological Reactive Sulfur Species.

A zinc dithiolate complex supported by a [N3S2] ligand was studied as a model for zinc-mediated thiolate-disulfide exchange, enabling isolation of a zinc-bound mixed-disulfide intermediate. Solution-phase characterization of this zinc-disulfide complex indicates an interaction between the zinc center and the disulfide moiety that results in activation of the S-S bond for subsequent reactions. Comparison of this reaction with disulfide exchange by a previously prepared zinc tetrasulfanido complex demonstrates that sulfane sulfur (S0) acts as an efficient thiolate trapping agent, that is, polysulfanide anions are much less basic than thiolates. The resulting polysulfanide anions also exhibit decreased nucleophilicity compared to the parent thiolate anions. Alkylation kinetics comparisons between the zinc dithiolate and zinc tetrasulfanido complexes indicate attenuation of zinc-bound thiolate nucleophilicity by sulfane. These results suggest a general interplay between zinc, sulfane, and thiol/thiolate reactivity that can significantly impact biological redox processes.

N-alkyl-β-ketoiminate zinc complexes: Synthesis, structure, and reactivity in ring-opening polymerization of lactide

A series of N-alkyl-β-ketoiminate monozinc complexes [{tBuCN(R)CHC(O)CtBu}2Zn] (R = Me, 2a; Et, 2b; Pr, 2c; iPr, 2d; Cy, 2e) were synthesized from the reaction of diethyl zinc with the corresponding β-ketimines. All these zinc complexes were characterized by NMR, elemental analysis and HRMS spectroscopy. The molecular structures of complexes 2b-2e were further confirmed by single-crystal X-ray diffraction. The structures exhibit that each zinc center is four-coordinate, and surrounded by two bidentate β-ketoiminate ligands, forming a distorted tetrahedral geometry. These homoleptic bis(β-ketoiminate) zinc complexes are active towards the ring-opening polymerization of rac-lactide in the absence of alcohol, yielding over 90 % conversions within 1 h at 70 °C in toluene with the ratio of monomer to catalyst being 100.

Selective hetero-bis-metalation of a cisoid isomer of doubly N-confused dioxohexaphyrin

Novel site-selective hetero-copper(II)/zinc(II) complexes of a cisoid-configured doubly N-confused dioxohexaphyrin analog (c-ZnCu-2 and c-CuZn-2) were synthesized and characterized. The resulting heterometal complexes exhibited a unique near-infrared (NIR) absorption feature, and the facile redox-active properties originated from the large 26[Formula: see text]-conjugated structure. The distinct difference between the site-dependent c-ZnCu-2 and c-CuZn-2appeared in the specific structural parameters of the d9 copper centers in the electron paramagnetic resonance spectra and the Lewis acidity of the zinc centers upon the base-titrations. These complexes have potential for the hetero-metal-containing [Formula: see text]-material applications that respond to the NIR light.

Direct Patterning of ZnO Deposition By Atomic-Layer Additive Manufacturing Using a Safe and Economical Precursor

AS-ALD has the potential to overcome many of the challenges the semiconductor industry is facing by enabling self-aligned fabrication, instead of lithography’s cost, resit, equipment. Main challenges in AS-ALD are the need for pre-patterned substrates, defects outside of the desired growing area resulting from insufficient selectivity, and limited selection of substrate materials that allow deposition. [1, 2]To overcome these challenges, we chose for the first time the novelty of direct patterning with an AL-3D printer, also called atomic layer additive manufacturing (ALAM). 3D-printing is a flexible and efficient tool for reducing the cost and time spend for designing and manufacturing. AL-3D in principle functions similar to conventional g-ALD and the special design of nozzle led in producing direct patterning. All the commercially available precursors which have been used in g-ALD are compatible with our invented equipment and not only we can produce the same films conveniently but also this device allows us to use new precursors e.g. Zn(DMP)2 opening a new chemistry window. We have already deposited different materials TiO2, Pt, SiO2, Al2O3 successfully using TTIP, (MeCp)PtMe3, APTES, TMA as precursor. The ZnO process is very well behaved in ALD community as a diethylzinc (ZnEt2) precursor’s very high vapor pressure and its very high reactivity to water. Our attempts at reducing the amount of vapor delivered were successful in part but the results were not sufficiently reproducible, therefore we turned to the use of a new zinc precursor instead.In this work we focus on the new precursor Zn(DMP)2 instead of ZnEt2 for ZnO deposition. The Zn(DMP)2 has a very low vapor pressure, the ethyl groups are complemented by dimethylamino substituents that stabilize central zinc ion and thereby render the molecule less reactive to water. Our characterization results shows the deposited ZnO films with our new precursor has same structure and composition as with ZnEt2 with a constant growth rate of 1.0 Å per cycle. the crystals are oriented in a roughly isotropic manner.After testing Zn(DMP)2 in classical ALD we achieved to print homogeneous patterns with well-defined edges and uniform thicknesses among the whole pattern. The rough particulate deposits indicative of uncontrolled CVD-mode deposition obtained with the ZnEt2 + water reaction are completely absent of lines obtained from the Zn(DMP)2 + water reaction. Furthermore, we fabricate a metal oxide transistor MOSFET to demonstrate the practical applications of the device. Clark; K. Tapily; K.-H. Yu; T. Hakamata; S. Consiglio; D. O´Meara; C. Wajda; J. Smith; G. Leusink; Perspective: New Process Technologies Required for Future Device and Scaling. APL Mater. 2018, 6, 05203Fang; J. C. Ho, Area-Selective Atomic Layer Deposition: Conformal Coating, Subnanometer Thickness Control, and Smart Positioning. ACS Nano 2015, 9 (9), 8651-8654.

A Charge-Neutral Self-Assembled L2Zn2 Helicate as Bench-Stable Receptor for Anion Recognition at Nanomolar Concentration.

The field of anion recognition chemistry is dominated by two fundamental approaches to design receptors. One relies on the formation of covalent bonds resulting in organic and often neutral host species, while the other one utilizes metal-driven self-assembly for the formation of charged receptors with well-defined nanocavities. Yet, the combination of their individual advantages in the form of charge-neutral metal-assembled bench-stable anion receptors is severely lacking. Herein, we present a fluorescent and uncharged double-stranded hydroxyquinoline-based zinc(II) helicate with the ability to bind environmentally relevant dicarboxylate anions with high fidelity in dimethyl sulfoxide (DMSO) at nanomolar concentrations. These dianions are pinned between zinc(II) centers with binding constants up to 145 000 000 M-1. The presented investigation exemplifies a pathway to bridge the two design approaches and combine their strength in one structural motif as an efficient anion receptor.

Understanding the reaction mechanism of the CO2 and cyclohexene oxide copolymerization catalyzed by zinc(II) and magnesium(II) catalysts: a DFT approach.

The reaction mechanisms of carbon dioxide and cyclohexene oxide copolymerization catalyzed by four different zinc(II)-magnesium(II) (labeled as M1-M2) catalysts were computationally studied using density functional theory at the BP86-D3(BJ)/def2-TZVP/SMD//BP86-D3(BJ)/def2-SVP/SMD level of theory. The results showed that the most effective catalyst was the ZnMg system, in which poly(cyclohexene carbonate) was the preferred product, followed by the side product cis-cyclohexene carbonate. The QTAIM, NCI and ELF analysis performed to understand the role of metals in the reaction showed that ligands and substrates interact more strongly with zinc(II) centers compared to magnesium(II) centers. Furthermore, the Zn-I interaction at the M1 position was stronger than the Mg-I interaction at the same position. All these results indicate a synergism between the metals Zn and Mg, which makes Zn(II)Mg(II) the best combination for the reaction.

Unexpected formation of two different coordination polymers from the reaction of Zn(HCOO)2·2H2O with 1,2-bis(4-pyridyl)ethylene

Zn(HCOO)2·2H2O reacts with 1,2-bis(4-pyridyl)ethylene (bpe) yielding two new coordination polymers [Zn4(HCOO)8(bpe)2(H2O)]∞ (1) and [Zn2(HCOO)4(bpe)]∞ (2) which were structurally characterized by IR spectroscopy and single crystal X-ray diffraction study. The hydrate species 1 is a 3D polymer where four different zinc sites are present, the first of them, four-coordinated, being linked by three bridging formate and one bridging bpe, the second six-coordinated, with a ZnNO5 coordination environment, almost regular, due to three bridging formate groups and one monodentate formate, one water molecule and one bpe. The third zinc center in 1 is always tetrahedral with three bridging formate ligands and one bridging bpe whereas the fourth Zn site is coordinated by five bridging formate ligands and one bridging bpe. The anhydrous species 2, obtained upon recrystallisation from DMF at 278 K is a zig-zag 1D polymer with a tetrahedral N2O2 zinc coordination environment due to two monodentate formate groups and two bridging bpe. Thermal analysis of 1 show a weight loss due to water elimination followed by formate and bpe decomposition, whereas in the case of 2 only a decomposition between 210 and 240 °C was observed.

Simple and Rapid Endotoxin Recognition Using a Dipicolylamine-Modified Fluorescent Probe with Picomolar-Order Sensitivity.

Endotoxin is a lipopolysaccharide (LPS) that is found in the outer membrane of the cell wall of Gram-negative bacteria. Due to its high toxicity, the allowable endotoxin limit for water for injection is set at a very low value. Conventional methods for endotoxin detection are time-consuming and expensive and have low reproducibility. A previous study has shown that dipicolylamine (dpa)-modified pyrene-based probes exhibit fluorescence enhancement in response to LPS; however, the application of such probes to the sensing of LPS is not discussed. Against this backdrop, we have developed a simple and rapid endotoxin detection method using a dpa-modified pyrenyl probe having a zinc(II) center (Zn-dpa-C4Py). When LPS was added into Zn-dpa-C4Py solution, excimer emission of the pyrene moiety emerged at 470 nm. This probe can detect picomolar concentrations of LPS (limit of detection = 41 pM). The high sensitivity of the probe is ascribed to the electrostatic and hydrophobic interactions between the probe and LPS, which result in the dimer formation of the pyrene moieties. We also found that Zn-dpa-C4Py has the highest selectivity for LPS compared with other phosphate derivatives, which is probably caused by the co-aggregation of the probe with LPS. We propose that Zn-dpa-C4Py is a promising chemical sensor for the detection of endotoxin in medical and pharmaceutical applications.

Efficient proton shuttle makes SazCA an excellent CO2 hydration enzyme

The fastest member of the carbonic anhydrase family catalysing the reversible hydration of carbon dioxide to bicarbonate ions has been recently reported to be SazCA. While thermostable, this enzyme shows exceptional activity at 353 K for the reaction. This study explores the molecular basis for the exceptional activity of SazCA, in contrast to SspCA, probed using molecular dynamics simulations. Our simulations, carried out at different temperatures, indicate the presence of efficient proton shuttle between the active zinc centre and His64 residue in the two enzymes. The proton accepting His64 residue was identified to have in and out conformations with the in conformations being supportive to proton acceptance. Our simulations show a large population of in conformations in SazCA making the enzyme exhibit an exceptional activity. The RMSF and H-bonds analysis confirmed the role of His2 and His207 in supporting the attainment of in conformations in SazCA resulting in exceptional activity. Communicated by Ramaswamy H. Sarma

Lithium, Magnesium, and Zinc Centers N,N′-Chelated by an Amine–Amide Hybrid Ligand

The synthesis and structure of lithium, magnesium, and zinc complexes N,N'-chelated by a hybrid amine-amido ligand ([2-(Me2NCH2)C6H4NR]-, abbreviated as LNR, where R = H, SiMe3, or Bn) are reported. The reaction of the least sterically demanding LNH with various magnesium sources gives the hexameric imide [LNMg]6 (4) by the elimination of n-butane from LNHMgnBu (2) or by the reaction of LNHLi (1) with MeMgBr. [LNH]2Mg (3) is obtained through the addition of 0.5 equiv of nBu2Mg or Mg[N(SiMe3)2]2 to LNH2 and with 1 equiv of nBu2Mg reacting to 2. Both LNHMgN(SiMe3)2 (6) and isostructural LNHZnN(SiMe3)2 (16) have been prepared using two different approaches: monodeprotonation of LNH2 by Zn/Mg[N(SiMe3)2]2 in a 1:1 ratio or ligand substitution of 2 or LNHZnEt (12) by 0.5 equiv of Sn[N(SiMe3)2]2. The reactions of 2 or 3 with 1 provide the heterotrimetallic complex [LNH]4Li2Mg (5). Benzyl- or trimethylsilyl-substituted anilines [LN(SiMe3)H (7) and LN(Bn)H (8)] with 0.5 equiv of nBu2Mg allow the formation of homoleptic bis(amides) of the [LN(R)]2Mg type (10 and 11). Nevertheless, only the silylated secondary amine 7 is able to provide the heteroleptic n-butylmagnesium amide LN(SiMe3)MgnBu (9) upon reaction with an equimolar amount of nBu2Mg. Similarly, 12, [LNH]2Zn (13), LN(R)ZnEt (17 and 18), and [LN(R)]2Zn [R = SiMe3 (19) and Bn (20)] were prepared by the monodeprotonation of LNH2 or LN(R)H using Et2Zn in the corresponding stoichiometric ratio. LNHZnI was prepared by the nucleophilic substitution of an ethyl chain in 12 by molecular iodine. A heterometallic complex, [LNH]4Li2Zn (14), analogous to 5 was prepared from 12 or 13 with 1 or 2 equiv of 1, respectively.