Homoleptic Compounds Research Articles

Synthesis, crystal structures, and NMR (1H, 13C) spectroscopy of PdII/HgII complexes with N, S-donor thiosemicarbazone/heterocyclic-2-thione ligands

The reaction of 2-benzoylpyridine thiosemicarbazone, {(C6H5)(py-N1)C2=N2-N3H-C1(=S)-N4H2, bzpytscH}, with palladium(II) chloride in acetonitrile yielded a heteroleptic complex, [Pd(N1,N2,S-bzpytsc)Cl] (1), in which the thio-ligand coordinated through pyridyl nitrogen (N1), azomethine nitrogen (N2) and sulfur as terdentate anion (N,N,S-bzpytsc–). In another reaction, pyrimidine-2-thione (pymtH) with mercury(II) chloride in CH3CN-DMF mixture formed a homoleptic compound, [Hg(N,S-pymt)2] (2), similar to the literature report of formation of a homoleptic compound, [Hg(κ1S-pyt)2], from HgCl2 and pytH in CH3CN-DMF. A reaction of mercury(II) bromide with pyridine-2-thione (pytH) in CH3CN-DMF mixture did not remove the bromides and rather yielded a heteroleptic complex of composition, [HgBr2(κ1S-pytH)2] (3). NMR (1H, 13C NMR) spectroscopy and infrared spectroscopy of 1–4 as well as crystal structures of 1, 3, and 4 are reported.

Structurally characterized aluminum alkoxide derivatives for aerosol spray materials production

The synthesis of a family of aluminum alkoxides was undertaken via the reaction of trimethyl aluminum (Al(CH3)3) using a series of sterically varied ortho-substituted phenols (H-OAr), including: 2-methyl phenol (H-oMP), 2-isopropyl phenol (H-oPP), 2-phenyl phenol (H-oPhP), 2,6-di-methyl phenol (H-DMP), 2,6-di-isopropyl phenol (H-DIP), and 2,6-di-phenyl phenol (H-DPhP). The products isolated using the least sterically encumbered phenoxides proved to generate the homoleptic compounds: [(oMP)Al((μ-oMP)2Al(oMP)2)2] (1), and [Al(μ-oPP)(oPP)2]2 (2), [Al(μ-oPP)(oPP)2(THF)]2 (2-THF), and [Al(μ-oPhP)(oPhP)2]2 (3). As the steric bulk was increased only partial substitution was achieved forming the alkyl, alkoxide compounds: [Al(μ-OAr)(CH3)(OAr)]2 (OAr = trans-DMP (4a), cis-DIP (5a), trans-DPhP (6a)). Sub-stoichiometric metathesis reactions for the smaller OAr ligands were undertaken to produce a series of [Al(CH3)3-x(OAr)x]2 where × = 2: OAr = trans-oMP (1a); x = 1, OAr = oMP (1b), and DMP (4b). Alternatively, the use of neo-pentanol (H-ONep) led to the homoleptic species [(ONep)Al((μ-ONep)2Al(ONep)2)2] (7) and heteroleptic [Al(μ-ONep)(CH3)2]2 (7b). Efforts to generate 7 from [Al(OPri)3]4 resulted in the production of the mixed ligated species [Al4(μ-OPri)6(ONep)6] (8). The compounds were fully characterized using a variety of analytical tools as well as multinuclear NMR (1H, 13C, 27Al) spectroscopy. Select species were used for aerosol spray pyrolysis for the anticipated production of alumina (Al2O3) materials. The final products from 1, 1b, 7, and 7b proved to generate amorphous mesoparticles of size 2.1(0.1), 2.6(0.2), 2.7(0.2), and 2.5(0.2) μm, respectively as determined by SEM and pXRD analyses. Data collected using Single Particle Aerosol Mass Spectrometry (SPAMS) revealed that Al0 particles had been produced instead of the expected Al2O3 ceramic materials.

Heteroleptic Iron(II) Spin-Crossover Complexes Based on a 2,6-Bis(pyrazol-1-yl)pyridine-type Ligand Functionalized with a Carboxylic Acid.

Two new heteroleptic complexes [Fe(1bppCOOH)(3bpp-bph)](ClO4)2·solv (1·solv, solv = various solvents; 1bppCOOH = 2,6-bis(1H-pyrazol-1-yl)isonicotinic acid; 3bpp-bph = 2,6-bis(5-([1,1'-biphenyl]-4-yl)-1H-pyrazol-3-yl)pyridine) and [Fe(1bppCOOH)(1bppCOOEt)](ClO4)2·0.5Me2CO (2·0.5Me2CO, 1bppCOOEt = ethyl 2,6-bis(1H-pyrazol-1-yl)isonicotinate) were designed and prepared. The heteroleptic compound 1·solv was obtained by the combination of stoichiometric amounts of Fe(ClO4)2, 1bppCOOH, and 3bpp-bph, and it was designed to fine-tune the spin crossover (SCO) properties with respect to the previously reported homoleptic compound [Fe(1bppCOOH)2](ClO4)2. Indeed, the introduction of a new substituted 3bpp ligand induces a weaker ligand field in addition to promoting the formation of π···π and C-H···π intermolecular interactions through the biphenyl groups. For the desolvated counterpart 1, this results in a shift of the SCO curve toward room temperature and the observation of a 13 K hysteresis width. Besides, compound 2·0.5Me2CO, which represents the first example of a heteroleptic complex containing two 1bpp tridentate ligands, stabilizes the LS state at room temperature confirming the same trend observed for the corresponding homoleptic compounds. Interestingly, both 1 and 2·0.5Me2CO heteroleptic complexes exhibit photoswitchable properties when irradiating with a 523 nm laser at 10 K. Preliminary characterization of the deposited complexes on native SiO2 by X-ray absorption measurements suggests oxidation and decomposition of the complexes.

Homoleptic and heteroleptic silver(I) complexes bearing diphosphane and thioamide ligands: Synthesis, structures, DNA interactions and antibacterial activity studies

Three silver(I) complexes bearing different combinations of diphosphanes and N-heterocyclic thioamides or thioamidates as ligands have been synthesized and structurally characterized: the ionic, homoleptic compound [Ag(xantphos)2][BF4] (1), where xantphos = 4,5-bis(diphenylphosphano)-9,9-dimethyl-xanthene, and the neutral, heteroleptic compounds [Ag(xantphos)(κ-S-pymt)] (2), where pymt = pyrimidine-2-thiolate, and [AgCl(dppbz)(κ-S-mtdztH)] (3), where dppbz = bis(diphenylphosphano)benzene and mtdztH = 5-methyl-1,3,4-thiadiazole-2-thione. X-ray crystallography studies reveal tetrahedral coordination environments around the silver(I) ions in compounds 1 and 3, while a trigonal planar arrangement of the P2S donor set has been found around the metal center in compound 2. The interaction of the three compounds with calf-thymus DNA was monitored by UV–vis spectroscopy, DNA-viscosity measurements and indirectly by testing their ability to compete with ethidium bromide for DNA intercalation sites studied by fluorescence emission spectroscopy. Intercalation was revealed as the most possible binding mode for the neutral compounds 2 and 3 and electrostatic interactions for the cationic complex [Ag(xantphos)2]+ in 1. Complexes 1–3 have also been found to display moderate in vitro antibacterial activity against the Gram-positive B. cereus, S. aureus and the Gram-negative E. coli bacterial strains, with the homoleptic bis-phosphane silver(I) compound 1 exhibiting a lower activity than the other two neutral compounds.

Are homoleptic complexes of ethylene with group 12 metals isolable in solution? A DFT study.

Ethylene efficiently binds late transition metals of groups 10 and 11. In spite of their reactivity, homoleptic compounds of formula [M-(η2-C2H4)3]n+ (with n = 0,1) have been isolated in solution and solid state and characterized spectroscopically throughout the last 50years with metals from groups 10 and 11. X-ray diffraction studies proved that such homoleptic adducts adopt planar "wheel" structures where ethylene moieties lies flat in the same plane both in group 10 and 11. These experimental findings were also confirmed by several in-depth computational investigations carried out to understand the bond pattern of such peculiar structures. Homoleptic complexes of group 10 and 11 metals with ethylene are normally obtained in poorly coordinating solvents (like CH2Cl2 or light petroleum) saturated with ethylene to increase the stability of such species in solution. In the case of coinage metals, Cu(I), Ag(I) and Au(I), weakly coordinating fluorinated counter-ions (like SbF6-) succeeded in stabilize the ethylene adducts, but, curiously, no analogous success has been reported for Zn(II), Cd(II), and Hg(II). Isoelectronic congeners along group 12 are still elusive, however, and, to our knowledge, full experimental and theoretical characterizations are still missing. This manuscript focuses on the theoretical study of the thermodynamic stability and properties of homoleptic complexes of ethylene with metals from group 12 in comparison with those from groups 10 and 11.

Alcoholysis of Al2(OtBu)6 – Synthesis and Crystal Structure of Al9O3(OEt)21

When Al2(OtBu)6 is treated with ethanol, Al9O3(OEt)21 (1) is obtained, which is a missing link in the series of polynuclear aluminum alkoxides. Alcoholysis of Al2(OtBu)6 in 2‐propanol yields the well‐known homoleptic compound Al4(OiPr)12 (2). As recently published, similar reactions with Fe2(OtBu)6 gave different structures. However, there are recurring structural patterns from alkoxide chemistry found. For a deeper understanding of this hardly predictable chemistry, compounds have to be correlated by such common structural motifs. We briefly report the syntheses of 1 and 2 and the crystal structure of 1. In addition, we provide an improved synthetic procedure for the preparation of the precursor Al2(OtBu)6. The structure of the new compound 1 is comprehensively compared to related structures from literature.

A Novel Bulky Heteroaromatic-Substituted Methanide Mimicking NacNac: Bis(4,6-tert-butylbenzoxazol-2-yl)methanide in s-Block Metal Coordination.

A novel bulky bis(4,6-tBu-benzoxazol-2-yl)methane ligand was synthesized in a straightforward three-step synthesis. The corresponding complexes [Li{(4,6-tBu-NCOC6 H2 )2 CH}THF], [K{η5 -(4,6-tBu-NCOC6 H2 )2 CH}]∞ , and [MgCl{(4,6-tBu-NCOC6 H2 )2 CH}(THF)2 ] were obtained upon metalation with alkaline or alkaline-earth-metal reagents. Reduction of [MgCl{(4,6-tBu-NCOC6 H2 )2 CH}(THF)2 ] with potassium metal or KC8 led to the formation of the homoleptic compound [Mg{(4,6-tBu-NCOC6 H2 )2 CH}2 ]. All compounds were fully characterized. Their solid-state structures as well as their behavior in solution, which was analyzed with the help of advanced NMR spectroscopic techniques, are discussed in detail.

Anionic Derivatives of Perfluorinated Trimethylgold.

The homoleptic compound [PPh4 ][CF3 AuCF3 ] cleanly undergoes photoinduced oxidative addition of CF3 I to afford the organogold(III) derivative [PPh4 ][(CF3 )3 AuI] in good yield and under mild conditions. This compound provides a convenient entry to the chemistry of the perfluorinated (CF3 )3 Au fragment, the properties of which were analyzed with the aid of DFT methods and compared with those of the homologous non-fluorinated (CH3 )3 Au moiety. It was found that reductive elimination of CX3 -CX3 in the former (X=F) requires a much higher energy barrier than in the latter (X=H) and is therefore considerably less favored. This can be considered as one of the main features underlying the significantly higher stability associated to the (CF3 )3 Au fragment and its derivatives. This unsaturated, 14-electron species can be stabilized by coordination of any of the halide ligands, including fluoride. In fact, the whole series of anionic [PPh4 ][(CF3 )3 AuX] complexes (X=F, Cl, Br, I, CN) has now been isolated and conveniently characterized. Evidence for intermolecular decomposition pathways upon thermolysis in the condensed phase is presented.

Coordination behavior of bis-phenolate saturated and unsaturated N-heterocyclic carbene ligands to zirconium: reactivity and activity in the copolymerization of cyclohexene oxide with CO2.

Tetravalent zirconium complexes supported by tridentate bis-phenolate imidazolidin-2-ylidene (L1), imidazol-2-ylidene (L2) and benzimidazol-2-ylidene (L3) NHC ligands were synthesized and evaluated as precursors for the copolymerization of cyclohexene oxide (CHO) with CO2. While the reactivity of the imidazolidinium [H3L1] chloride salt with Zr(OiPr)4(HOiPr), and subsequent ligand exchanges with either (CH3)3SiCl or LiOiPr lead to a series of heteroleptic compounds (κ3-O,C,O-L1)Zr(X)2(THF) (X = Cl, OiPr), both imidazolium [H3L2] and benzimidazolium [H3L3] chloride salts give a mixture of homoleptic (κ3-O,C,O-NHC)2Zr and zwitterionic (κ2-O,O-HL)ZrCl2(OiPr) compounds along with traces or the absence of the heteroleptic intermediate (κ3-O,C,O-NHC)Zr(Cl)(OiPr)(THF). Such dissimilar reactivity between the unsaturated and saturated NHC ligands is predominantly ascribed to the increased acidity of azolium salts along with the π-donor strength of the Ccarbene in L2 and L3-Zr moieties. The reactivity with the more acidic azolium salts (H3L2/3) and the destabilized Zr-Xtrans to NHCcarbene bond results in a significant increase in the amount of homoleptic compounds generating HCl. The released HCl reacts preferentially with the heteroleptic intermediates having non-planar NHC ligands (i.e. L2/3) promoting the formation of zwitterionic complexes. The in situ deprotonation of the isolated zwitterionic (κ2-O,O-HL3)ZrCl2(OiPr) compound by using Ag2O gives the homoleptic complex as the major component along with a bimetallic hydroxo-bridged [(κ3-O,C,O-L3)Zr(μ-OH)(OiPr)]2 compound. Of particular interest is that only the heteroleptic NHC-Zr(iv) complexes were identified to be active and highly selective towards the copolymerization of CHO with CO2 independently of the co-catalysts used (both anionic and neutral) under mild conditions (PCO2 < 1 bar, T = 60 °C), and gave atactic and completely alternating copolymers in a controlled manner (Mw/Mn ≈ 1.3-1.8). In contrast, the isolated homoleptic, zwitterionic and bimetallic zirconium species were found to be inactive under similar reaction conditions. Although the activity found for NHC-Zr(iv) complexes is nearly of the same order of magnitude as that of the NHC-Ti(iv) analogues, these results are the first examples of tetravalent zirconium complexes achieving high selectivity (99% in PCHC) in the catalyzed copolymerization of CHO with CO2.

Ligand effects in a heteroleptic bis-tridentate iron(iii) spin crossover complex showing a very high T1/2 value.

We describe the first example of a bis-tridentate heteroleptic iron(iii) spin crossover (SCO) complex, [Fe(3-OMe-SalEen)(thsa)]. Compared to the parent homoleptic compounds, the spin crossover features in the heteroleptic species are enhanced with a gradual-abrupt spin transition at 344 K. Clear correlations between π-π interactions and the T1/2 value have been revealed.

Electronic structure and spectroscopy of homoleptic compounds of dimolybdenum using TDDFT

Ten compounds of dimolybdenum are studied using density functional theory and time-dependent density functional theory. The energy of the strongest symmetry-allowed bands is calculated. The results are then compared with experimental data, when available. The PW91 functional gives results for geometry and for the energy of the δ→δ* band that show good agreement with experimental data. However, the B3LYP functional gives more realistic values for the whole spectrum when the results are compared with experimental data. Finally, the different values of energy of these bands are explained analyzing the molecular orbitals involved in these transitions. Some ligands can act as an unsaturated system in conjugation with the delta bond, modifying the energies of the electronic transitions.

Charge conduction study of phosphorescent iridium compounds for organic light-emitting diodes application

The charge conduction properties of a series of iridium-based compounds for phosphorescent organic light-emitting diodes (OLEDs) have been investigated by thin-film transistor (TFT) technique. These compounds include four homoleptic compounds: Ir(ppy)3, Ir(piq)3, Ir(Tpa-py)3, Ir(Cz-py)3, and two heteroleptic compounds Ir(Cz-py)2(acac) and FIrpic. Ir(ppy)3, Ir(piq)3 and FIrpic are commercially available compounds, while Ir(Tpa-py)3, Ir(Cz-py)3 and Ir(Cz-py)2(acac) are specially designed to test their conductivities with respect to the commercial compounds. In neat films, with the exception of FIrpic, all Ir-compounds possess significant hole transporting capabilities, with hole mobilities in the range of about 5×10−6–2×10−5cm2V−1s−1. FIrpic, however, is non-conducting as revealed by TFT measurements. We further investigate how Ir-compounds modify carrier transport as dopants when they are doped into a phosphorescent host material CBP. The commercial compounds are chosen for the investigation. Small amounts of Ir(ppy)3 and Ir(piq)3 (<10%) behave as hole traps when they are doped into CBP. The hole conduction of the doped CBP films can be reduced by as much as 4 orders of magnitude. Percolating conduction of Ir-compounds occurs when the doping concentrations of the Ir-compounds exceed 10%, and the hole mobilities gradually increase as their values reach those of the neat Ir films. In contrast to Ir(ppy)3 and Ir(piq)3, FIrpic does not participate in hole conduction when it is doped into CBP. The hole mobility decreases monotonically as the concentration of FIrpic increases due to the increase of the average charge hopping distance in CBP.

Facile formation of homoleptic Au(III) trications via simultaneous oxidation and ligand delivery from [PhI(pyridine)2](2+).

We report the first examples of Au(III) tricationic complexes bound only by neutral monodentate ligands, which are a new class of gold reagents. Oxidative addition to the bis-pyridine Au(I) cation, [Au(4-DMAP)2](+), using a series of dicationic I(III) oxidants of the general form [PhI(L)2](2+) (L = pyridine, 4-DMAP, 4-cyanopyridine) allows ready access to homoleptic and pseudo-homoleptic Au(III) complexes [Au(4-DMAP)2(L)2](3+). The facile oxidative addition of Au(I) species additionally demonstrates the efficacy of PhI(L)2](2+) reagents as halide-free oxidants for Au(I). Comparisons are made via attempts to oxidize NHC-Au(I)Cl, where introduction of the chloride anion results in complex mixtures via ligand and chloride exchange, demonstrating the advantage of using the pyridine-based homoleptic compounds. The new Au(III) trications show intriguing reactivity with water, yielding dinuclear oxo-bridged and rare terminal Au(III)-OH complexes.

Heteroleptic Precursors for Atomic Layer Deposition

As the atomic layer deposition (ALD) method is based on sequential, self-limiting surface reactions the precursor chemistry is the key to a successful processing of conformal high quality thin films. ALD precursor chemistry has traditionally been based on homoleptic compounds such as, but not limited to, metal halides, alkylamides and alkoxides. However, these precursors sometimes have drawbacks such as possible halide contamination and low thermal stabilities. Consequently, heteroleptic precursors have been investigated as alternatives to the existing homoleptic counterparts, leading to the development of several advantageous processes. Here, examples of heteroleptic precursors for ALD processes of transition metals and their oxides are given. Special focus is given to oxides of the rare earths and groups 4 and 5. Trends in the properties of heteroleptic precursors are discussed. Several examples of our recent results are shown, including introduction of novel processes based on amidinate-cyclopentadienyl complexes for ALD of rare earth oxides.

Heteroleptic Precursors for Atomic Layer Deposition

As the atomic layer deposition (ALD) method is based on sequential, self-limiting surface reactions the precursor chemistry is the key to a successful processing of conformal high quality thin films. ALD precursor chemistry has traditionally been based on homoleptic compounds such as, but not limited to, metal halides, alkylamides and alkoxides. However, these precursors may have drawbacks such as possible halide contamination and low thermal stabilities in the case of the alkylamides and alkoxides. Consequently, heteroleptic precursors have been investigated as alternatives to the existing homoleptic counterparts, leading to the development of several advantageous processes.In the recent years, increasing research effort has been dedicated in development of novel ALD processes focusing especially on transition metals and their oxides using heteroleptic precursors. Interestingly, heteroleptic compounds often show different properties than their homoleptic counterparts. One type of ligand can provide reactivity and another stability, thus widening the process window with comparable film growth rate.In this presentation heteroleptic precursors for ALD processes of transition metals and their oxides will be reviewed. Special focus is given to oxides of the rare earths and groups 4 and 5. Trends in the properties of heteroleptic precursors are discussed. Several examples of our recent results are shown, including introduction of novel processes based on amidinate-cyclopentadienyl complexes for ALD of rare earth oxides.

Atomic Layer Deposition of Groups 4 and 5 Transition Metal Oxide Thin Films: Focus on Heteroleptic Precursors

The atomic layer deposition (ALD) process, an alternative to CVD, is universally appreciated for its unique advantages such as excellent repeatability, conformity, and thickness control at the atomic level. ALD precursor chemistry has mainly been based on homoleptic compounds such as, but not limited to, metal halides, alkylamides, and alkoxides, however these precursors have drawbacks such as possible halide contamination and low thermal stabilities in the case of the alkylamides and alkoxides. Consequently, heteroleptic precursors have been investigated as alternatives to the existing homoleptic counterparts, leading to the development of several advantageous processes. Nevertheless, there is no thematic review dedicated to the heteroleptic precursors and their properties, and it seems that no coherent strategy has been adopted for the development of heteroleptic precursors. This review gives a brief description of ALD and presents studies on the deposition of thin films of groups 4 and 5 metal oxides using ALD. A description of the general ALD properties of homoleptic precursors, in addition to a review on the thermal ALD of groups 4 and 5 metal oxides from heteroleptic precursors, is provided. Trends in the properties of heteroleptic ALD precursors, based on the literature review and recent experimental data, are discussed.

Heteroleptic Group 2 Metal Precursors for Metal Oxide Thin Films

AbstractA new class of heteroleptic complexes of calcium, strontium, and barium have been synthesized using 1‐{[2‐(dimethylamino)ethyl](methyl)amino}‐2‐methylpropan‐2‐ol (demampH) and 2,2,6,6‐tetramethyl‐3,5‐heptanedione (tmhdH). Complexes [{Ca(demamp)(tmhd)}2] (4), [{Sr(demamp)(tmhd)}2] (5), and [{Ba(demamp)(tmhd)}3] (6) were prepared in two‐step processes. Partially substituted complexes [{Ca(demamp)(btsa)}2] (1), [{Sr(demamp)(btsa)}2] (2), and [{Ba(demamp)(btsa)}2] (3) [btsa = bis(trimethylsilyl)amide] were isolated and characterized. The molecular structures of all the compounds were studied by single‐crystal X‐ray crystallography. The strontium and calcium complexes have dimeric configuration with bridging of two alkoxide oxygen atoms between the metals, whereas the barium complex is a trimer. Complexes 4 and 5 show higher volatility and thermal stability with respect to the homoleptic compounds, while barium complex 6 is unstable. The TG analyses of compounds 4 and 5 display one‐step curves with 9.0 and 9.6 % residue at 375 and 370 °C, respectively.

Gold(i) complexes with heteroaryl phosphine ligands

Gold(I) complexes ligated by phosphines with N-heterocycles in the periphery were prepared. First the synthesis of the ligands N-(diphenylphosphino)-4-(pyridin-2-yl)pyrimidin-2-amine (Hpypya) and N-(diphenylphosphino)-4-phenylpyrimidin-2-amine (Hphpya) are reported. These two compounds together with the related but earlier published ligands 3-(2-(diphenylphosphino)phenyl)-1H-pyrazole (Hph3py) and 5-(4-(diphenylphosphino)phenyl)-1H-pyrazole (Hph5py) were reacted with [(tht)AuCl] and [Au(tht)2]ClO4 to give the heteroleptic complexes [(L)AuCl] and the homoleptic compounds [(L)2Au]ClO4 (L = Hpypya, Hphpya, Hph3py, and Hph5py). Single crystal X-ray diffraction studies revealed that the heteroleptic complexes form hydrogen bonds between two N-heterocycles of neighboring complexes resulting in dimeric structures. The homoleptic complexes show a different behavior.

The synthesis and structure of [Zn(TEMPO)2]2 and [Zn(μ-H)(μ(2)-η(1):η(1)-TEMPO)]6.

The commercially available radical TEMPO (2,2,6,6-tetramethylpiperidin-1-yloxy) reacts with [ZnCp*2] (1) to yield the homoleptic compound [Zn(TEMPO)2]2 (2) through coupling of two Cp* radicals. Compound 1 reacts with H2 to afford the hydride complex [Zn(μ-H)(μ(2)-η(1)-η(1)-TEMPO)]6 (3) featuring a planar Zn6H6 ring in the solid state. Preliminary data suggest that the formation of 3 proceeds via a radical mechanism.

Alkaline Earth Complexes of Silylated Aminopyridinato Ligands: Homoleptic Compounds and Heterobimetallic Coordination Polymers

The synthesis and characterization of magnesium and calcium complexes of sterically demanding aminopyridinato ligands is reported. The reaction of the 2-Me3SiNH-6-MeC5H3N (L(1)H), 2-MePh2SiNH-6-MeC5H3N (L(2)H), and 2-Me3SiNH-6-PhC5H3N (L(3)H) with KH in tetrahydrofuran (THF) yielded potassium salts L(1)K(thf)0.5 (1), L(2)K (2), and L(3)K(thf)0.5 (3), which, through subsequent reaction with MgI2 and CaI2, afforded the homoleptic complexes (L)2Ae(thf)n [L = L(1), Ae = Mg, n = 1 (4); L = L(2), Ae = Mg, n = 0 (5); L = L(3), Ae = Mg, n = 0 (6); L = L(2), Ae = Ca, n = 2 (7)] and heterobimetallic calciates {[(L)3Ca]K}∞ [L = L(1) (8); L = L(2) (9)]. The solid state structure of 8 reveals a polymeric arrangement in which the calciate units are interlocked by bridging potassium ions. Metalation reactions between L(1)H or L(2)H and ((n)Bu)2Mg lead to the solvent-free compounds (L)2Mg [L = L(1) (10); L = L(2) (5)]. The bridged butyl mixed-metal complex [(L(1))Li(μ2-(n)Bu)Mg(L(1))]∞ (11) was also obtained via a cocomplexation reaction with (n)BuLi and ((n)Bu)2Mg. 11, which adopts a monodimensional polymeric array in the solid state, is a rare example of an alkyl-bridged Li/Mg complex and the first complex to feature an unsupported bridging butyl interaction between two metals. Changing the cocomplexation reaction conditions, the order of reagents added to the reactions mixture, and with the use of a coordinating solvent (tetrahydrofuran) formed the magnesiate complex (L(1))3MgLi(thf) (12).