Quantum theory of the structure and bonding in proteins : Part 15. The threonine dipeptide

The energies of the conformations of the threonine dipeptide are determined by adding the energetic effects of the methyl group to the results for the serine dipeptide. The results are then checked by explicit ab initio molecular orbital computations on the important low-energy conformations. Analysis of these results yields the non-bonded repulsions, the torsion barriers and the hydrogen bonds.

There are many similarities between the serine results and those for threonine. In particular, the computations show that the +60° value of χ ₁ is again important in the helix bridge region of the Ramachandran map. On the other hand, there is a pronounced difference between serine and threonine in that the methyl group of the latter causes the form with χ₁ = 180° to be a high-energy conformation over all areas of the Ramachandran map except the left sheet region. These and other points are in accord with the experimental data for five proteins.     

Ca-mediated thiolysis of peptide–resin linkage as an option for preparing protected peptide thioesters

A mild new procedure for preparing protected peptide thioesters, based on Ca²⁺-assisted thiolysis of peptide–Kaiser oxime resin (KOR) linkage, is described. Ac-Ile-Ser(Bzl)-Asp(OcHx)-SR (Ac: acetyl; Bzl: benzyl; cHx: cyclohexyl), model peptide, was readily released from the resin by incubating the peptide–KOR at 60 °C in mixtures of DMF with n-butanethiol [R = (CH₂)₃CH₃] or ethyl 3-mercaptopropionate [R = (CH₂)₂COOCH₂CH₃] containing Ca(CH₃COO)₂. After serine and aspartic acid side-chain deprotection under acid conditions, Ac-Ile-Ser-Asp-S(CH₂)₂COOCH₂CH₃ was successfully obtained with good quality and high yield. This type of C-terminal modified peptide may act as an excellent acyl donor in peptide segment condensation by the thioester method, native chemical ligation and enzymatic methods.     

Structure cristalline et conformation en solution aqueuse de la carnosine (β-alanyl-L-histidine)

Carnosine (β-alanyl-L-histidine) is a biologically active molecule involved in muscular metabolism. It crystallises in the C; space group with a = 24.725 Å b = 5,427 Å c = 8,004 Å β = 100,2° (Z = 4)

In the crystal, acid and basic groups are engaged in hydrogen bonds whose strength is evaluated through IR frequencies. Molecular conformation in the solid state is defined by τ₁ = /t-177° τ₂ = −38° φ = −96° ψ = +131° χ₁ = 181° χ₂₁ = 62°

NMR study of carnosine in aqueous solution indicates that rotation about CH₂-CH₂ is free and that the other angles take the following values: Ø −150° or −90° and X₁ = 165° or 315°. Infrared and Raman spectra suggest that τ₂ undergoes small changes when going from crystal to solution while ψ is close to +150°.     

Structural and spectral studies on N-(4-chloro)benzoyl-N′-(4-tolyl)thiourea

The crystal and molecular structure of the N-(4-chloro)benzoyl-N′-(4-tolyl)thiourea (C₁₅H₁₃N₂OSCl, M_r=304.79) is determined by X-ray diffraction. The crystal structure is monoclinic, space group: P2₁/n, a=16.097(6), b=4.5989(2), c=19.388(7) Å and β=89.299(6)° V=1434.7(9)ų, Z=4. FTIR and NMR spectra have been characterized. The interactions of intramolecular and intermolecular hydrogen bonds have been discussed. Density functional theory (DFT) (B3LYP) methods have been used to determine the structure and energies of stable conformers. Minimum energy conformations are calculated as a function of the torsion angle θ (C13–N1–C14–N2) varied every 30°. The optimized geometry corresponding to crystal structure is the most stable conformation. This has partly been attributed to intramolecular hydrogen bonds. With the basis sets of the 6-311G* quality, the DFT calculated bond parameters and harmonic vibrations are predicted in a very good agreement with experimental data.     

Three interpenetrated frameworks constructed by long flexible N,N′-bipyridyl and dicarboxylate ligands

Three interpenetrated polymeric networks, {[Co(bpp)(OH-BDC)] · H₂O}_n (1) [Ni(bpp)_1.5(H₂O)(OH-BDC)]_n (2) and {[Cd(bpp)(H₂O)(OH-BDC)] · 2H₂O}_n (3), have been prepared by hydrothermal reactions of 1,3-bis(4-pyridyl)propane (bpp), 5-hydroxyisophthalic acid (OH-H₂BDC), with Co(NO₃)₂ · 6H₂O, Ni(NO₃)₂ · 6H₂O and Cd(NO₃)₂ · 4H₂O, respectively. Single-crystal X-ray diffraction analyses reveal that the three compounds all exhibit interpenetrated but entirely different structures. Compound 1 is a fourfold interpenetrated adamantanoid structure with water molecules as space fillers, in which bpp adopts a TG conformation (T = trans, G = gauche). Compound 2 is an interdigitated structure from the interpenetrated long arms of one-dimensional molecular ladders, while bpp in 2 adopts both TT and TG conformations. Compound 3 is a twofold interpenetrated three-dimensional network from a one-dimensional metal-carboxylate chain bridged by TG conformational bpp. The hydrogen bonding interactions in 1–3 further stabilize the whole structural frameworks and play critical roles in their constructions.     

An ab initio close-coupling calculation of the lower vibrational energies of the HCl dimer

We have previously determined an analytical ab initio six-dimensional potential energy surface for the HCl dimer, and in the present paper we use this potential, with the HCl bond lengths held fixed, in a full (four-dimensional) close-coupling calculation to determine the energies of the lowest 24 vibrational states. These vibrational states involve the intermolecular stretch ν₄, the trans-bend tunneling vibration ν₅, and the torsion ν₆. The highest of the 24 levels is the (ν₄ν₅ν₆)=(111) state, for which we calculate an energy of 200 cm⁻¹ above the (000) state. As well as determining tunneling energies up to 5ν₅=183 cm⁻¹, we determine ν₄=49 cm⁻¹, 2ν₄=93 cm⁻¹, 3ν₄=134 cm⁻¹, 4ν₄=172 cm⁻¹, ν₆=137 cm⁻¹ and ν₄+ν₆=178 cm⁻¹, together with tunneling energies in all these states. Making allowance for the HCl stretching zero-point energy we determine the dissociation energy D₀ as 390 cm⁻¹ on this analytical surface. We determine that below 300 cm⁻¹ there are 72 vibrational (J=K=0) states, and below dissociation there are 162 vibrational (J=K=0) states, for this potential surface.     

Study of the N2 bΠu state via 1 + 1 multiphoton ionization

Medium-resolution spectra of the N₂ b¹Π_u-X¹Σ_g⁺ band system were recorded by 1 + 1 multiphoton ionization. In the spectra we found different linewidths for transitions to different vibrational levels in the b ¹Π_u state: Δν₀ = 0.50 ± 0.05 cm⁻¹, Δν₁ = 0.28 ± 0.02 cm⁻¹, Δν₂ = 0.65 ± 0.06 cm⁻¹, Δν₃ = 3.2 ± 0.5 cm⁻¹, Δν₄ = 0.60 ± 0.07 cm⁻¹, and Δν₅ = 0.28 ± 0.02 cm⁻¹. From these linewidths, predissociation lifetimes τ_ν were obtained: τ₀ = 16 ± 3 ps, τ₁ > 150 ps, τ₂ = 10 ± 2 ps, τ₃ = 1.6 ± 0.3 ps, τ₄ = 9 ± 2 ps, and τ₅ > 150 ps. Band origins and rotational constants for the b ¹Π_uν = 0 and 1 levels were determined for the ¹⁴N₂ and ¹⁴N¹⁵N molecules.     

Ab initio calculations on blocked Pro-Ala dipeptides

The effect of the chirality of the amino acid at position i + 2 on a β-turn was investigated by a grid scan ab initio calculation on the Ac- -Pro- -Ala-NH₂ and Ac- -Pro- -Ala-NH₂ blocked dipeptides. Th6-31G basis set was used to estimate the effect of the alanyl side chain on the conformation of the peptide backbone in a blocked dipeptide as a simple, but complete model for a reverse turn. This study provides a quantum mechanical evaluation of the ability of the NH at the i + 3 residue to form the H-bond that closes the 10 membered ring which stabilizes the turn. The lowest energy of all 64 probed conformations of the -Ala containing peptide corresponded to a good type II β-turn with a hydrogen bond distance between the acetyl oxygen and the amide terminal hydrogen of 2.21 Å. A comparison with the nonblocked dipeptide ab initio study indicates that the presence of the end blocks enhances the propensity of the -Ala-containing dipeptide for a type II β-turn, but does not seem to enhance the propensity of the -Ala-containing dipeptide for a type I β-turn. The energies and geometric parameters for the lowest four optimized conformations identified by the grid scan search for each molecule have been calculated.     

Synthesis and crystal structure of two novel nickel (imidazole) complexes having hydrogen-bonded networks

Two nickel (imidazole) complexes, Ni(im)₆Cl₂·4H₂O (1) and Ni(im)₆(NO₃)₂ (2) (im=imidazole) have been synthesized and characterized by elemental analysis, IR, UV, TG and single crystal X-ray diffraction. 1 crystallizes in the triclinic space group P-1 with a=8.800(6) Å, b=9.081(6) Å, c=10.565(7) Å, =75.058(9)°, β=83.143(8)°, γ=61.722(8)°, V=718.3(8) Å³, Z=1 and R₁ (wR₂)=0.0469 (0.1497). 2 crystallizes in the trigonal space group R-3 with a=12.370(6) Å, b=12.370(6) Å, c=14.782(14) Å, =90.00°, β=90.00°, γ=120.00°, V=1959(2) Å³, Z=3 and R₁ (wR₂)=0.0358 (0.0955). 1 and 2 exhibit different supramolecular network due to their different counter anions and different hydrogen bonding connection. In compound 1, [Ni(im)₆]²⁺ cation and counter anions Cl⁻ alternatively array in an ABAB fashion via N–HCl hydrogen bonding. In compound 2, the plane of each NO₃²⁻ is almost parallel and each NO₃²⁻ connect three different [Ni(im)₆]²⁺ cations via N–HO hydrogen bonding.     

液态聚乙二醇CH_2剪切振动和扭转振动——拉曼光谱和密度泛函理论计算

提出了一种新方案,以有效洞察液态中共存构象异构体对聚氧乙烯(PEO)实际振动光谱的贡献。通过定义6种-(CH_2CH_2O)-重复单元构象,构建并优化得到4种全同EO构象组合[(TGT)_(10)、(TTT)_(10)、(TTG)_(10)和(GTG)_(10)]和3种其它EO构象组合的构象异构体结构,并在PCM溶剂模型和B3LYP/6-31G(d)理论水平下,对结构进行了优化和振动频率计算。通过振动模式分析,提出描述PEO400各构象异构体的不同CH_2剪切振动和CH_2扭转振动模式的统一标准,确定了4种CH_2CH_2-O-CH_2CH_2链段构象和相关振动模式,以及它们与振动频率大小的关系,并应用于实际拉曼光谱的指认。     

Syntheses and structural characterization of trivalent lanthanide complexes of p-sulfonatothiacalix[4]arene

The X-ray crystallographic studies are reported for the water-soluble trivalent lanthanide complexes of the macrocyclic p-sulfonatothiacalix[4]arene [Gd(H₂O)₆((CH₃)₂SO)(p-sulfonatothiacalix[4]arene)]·H₃O⁺·5H₂O (1) and Na[Nd(H₂O)₆((CH₃)₂SO)(p-sulfonatothiacalix[4]arene)]·3H₂O (2). The complexes are isostructural and belong to monoclinic system, C2/m space group. The Ln³⁺ metal ion is coordinated by the thiacalixarene ligand via the sulfonato group, and also ligated by an oxygen atom of a dimethyl sulfoxide (DMSO) molecule that occupies the cavity of the thiacalixarene and six aqua ligands. The thiacalixarenes are linked by the coordinated water molecules through hydrogen bonding to form a 2D polymer. The p-sulfonatothiacalixarenes maintain the clay-like bi-layer structure in the coordination network.     

Microwave spectrum and rotational isomers of ethyl fluoroformate

The microwave spectrum of ethyl fluoroformate displays strong a-type R branch transitions from two rotameric forms. One species (extended form) has rotational constants A₀ = 9191.3(9) MHz, B₀ = 2112.61(1) MHz, C₀ = 1756.73(1) MHz which are consistent with a syn-anti (τ₁(OCOC) = 0°, r₂(cocc) = 180°) planar heavy atom structure. The second species (compact form) has rotational constants A₀ = 7760(3) MHz, B₀ = 2388.38(4) MHz, C₀ = 2102.47(3) MHz which are consistent with a syn-gauche (τ₁(ococ) = 0°, τ₂(cocc) ˜ 90°) structure. The two conformational forms have approximately equal energy (0 ± 40 cm⁻¹). Four vibrational satellites of the extended species have been analyzed yielding a torsional frequency around the O-ethyl bond of 70(10) cm⁻¹. Three vibrational satellites attributed to the O-ethyl torsion of the compact species have been analyzed yielding a vibrational frequency of 90(10) cm⁻¹. Approximate Fourier coefficients of a three term potential function for internal rotation about the O-ethyl bond have been determined. Vibrational satellites attributed to the first excited states of the O-ester torsion have been analyzed for both conformers. The torsional vibrational frequency around the O-ester bond is 110(15) cm⁻¹ for the extended conformers and 120(20) cm⁻¹ for the compact.     

Photoredox behaviour of trans and cis Co (III)-diisothiocyanatotetram(m)ine complexes

The trans and cis isomers of Co(NCS)₂(NH₃)₄⁺ and Co(NCS)₂(en)₂⁺ were prepared and characterized. Single-crystal X-ray diffraction showed that the first named was the trans isomer and established that the thiocyanates are N bonded. Photoredox quantum yields of the Co²⁺ ion on room temperature irradiation at 360 nm were found to be 0.065±0.001, 0.0082±0.001, 0.0088±0.0007 and 0.0040±0.0010 respectively. Other products measured were the thiocyanate ion and ammonia, but the relationships of these yields to Co²⁺ were not as expected for simple oxidation of thiocyanate and reduction of Co(III). On irradation in the presence of thiocyanate, a significant increase in yields occurs and this can be modelled in terms of scavenging of the thiocyanate radical from an initial caged radical pair giving picosecond estimates for the lifetime of this species of the order of tens of picoseconds, or in terms of photolysis of a thiocyanate/complex ion pair giving formation constant of 0.25±0.17, 0.12±0.04, 0.11±0.06 and 0.06±0.04 for the complexes in the sequence above. In all but the last instance these are in excellent agreement with the values estimated by fitting the thiocynate induced changes in the UV-visible spectra of the complexes, 0.34±0.25, 0.14±0.07, 0.09±0.07 and 0.60±0.07 respectively. Laser flash photolysis studies on the nanosecond and picosecond time-scale failed to reveal any direct spectroscopic evidence for a radical pair species, but the absorbance of (NCS)₂^-√ was seen in all four systems. The effects of added electrolytes and of viscosity on the formation and decay of this intermediate were investigated and are reported in detail.     

Influence of protonation on crystal packing and thermal behaviour of tert-butylammonium decavanadates

Two tert-butylammonium decavanadate(V) salts with the formulae [(CH₃)₃CNH₃]₆[V₁₀O₂₈] · 8H₂O (1) and [(CH₃)₃CNH₃]₄[H₂V₁₀O₂₈] (2), have been synthesized and their crystal structures have been determined by means of single-crystal X-ray diffraction. The crystal structure of compound 1 is stabilized by electrostatic forces and an extensive network of hydrogen contacts involving anions, cations and water molecules. The anions and cations of this compound are arranged in layers perpendicular to the [010] direction following the sequence, cation-anion-cation. In the crystal structure of compound (2), each dihydrogen decavanadate(V) anion is joined to three adjacent polyanions by means of O(6)---H ··· O(4) hydrogen contacts forming layers parallel to the plane ( 01) and the hydrophobic groups of the cations are disposed in layers parallel to the anionic sheets. The thermal behaviour of both compounds has been studied. Compound 1 is an octahydrate and its thermal decomposition begins at 70°C with the loss of water of crystallization, while compound 2 is anhydrous and is consequently more stable, with decomposition starting at 200°C.     

Computational analysis of side-chain conformations in polyaspartates exhibiting reversible helical sense inversion in the solid state

Poly(β-phenylpropyl -aspartate), poly(β-phenylbutyl -aspartate), and poly(β-phenylpentyl -aspartate) exhibit a reversible transformation from a right-handed -helix (_R) to a left-handed ω-helix (ω_L) in the solid state. During this transition, the infrared (IR) dichroism of the side-chain ester group and the birefringence change drastically, showing that the side-chain conformations are different for these two helices. In the present study, for the purpose of elucidating the preferred side-chain conformation in each helix, we performed the computational analyses. The energy contours, the directions of the IR transition moments and the anisotropies in polarizability as functions of the first two dihedral angles of the side chain, χ₁ and χ₂ were calculated. Then, comparing them with the experimental IR dichroism and birefringence data, we elucidated the specific side-chain conformation preferred for each _R or ω_L skeleton. The preferred values of (χ₁, χ₂) were found to be (−75, −60°) for _R and (180, 45°) for ω_L.     

Molecular determinants for drug-receptor interactions Part 14. X-ray molecular structure and theoretical conformational (MNDO, MM2) studies of the narcotic dualist buprenorphine hydrochloride

The X-ray molecular structure of buprenorphine hydrochloride [(C₂₉H₄₂O₄N)⁺Cl⁻] was determined. The molecule forms colourless tetragonal crystals; the space group is P4₁2₁2₁ with eight molecules per unit cell of dimensions a = 11.507(2) Å and c = 41.952(9) Å. The structure was determined by direct methods and refined by the full-matrix least-squares procedure to R = 0.056 for 2251 observed reflections. The protonated buprenorphine (BPNH⁺) in the solid state adopts the T-shape form typical of benzomorphan compounds; the substituent group at the N atom is in the equatorial configuration and the cyclopropylmethyl side-chain is almost perpendicular to the piperidine ring. Theoretical studies of the conformations and the rotational energetics of BPNH⁺ were performed using both the semiquantitative MNDO and the force field (MM2) methods. The latter method predicted four low energy conformations about the N-C(21) and C(21)-C(22) bonds. Two of these were more significantly populated (59% and 30%). They may easily interconvert through only a single torsional process. The less-populated (30%) conformation was consistent with that adopted in the solid state. The MNDO method predicted different low energy conformations of the N-cyclopropylmethyl moiety. Neither method reproduced the favoured torsional angles adopted by the structurally analogous naltrexone molecule which has the opposite pharmacological profile.     

Large heteropolymetalate complexes formed from lanthanide (Y, Ce, Pr, Nd, Sm, Eu, Gd), nickel cations and cryptate [As4W40O140]: synthesis and structure characterization

A new family of heteropolytungstate complexes (NH₄)₂₁[Ln(H₂O)₅{Ni(H₂O)}₂As₄W₄₀O₁₄₀]·xH₂O(Ln=Y, Ce, Pr, Nd, Sm, Eu, Gd) were prepared by the reaction of Na₂₇[NaAs₄W₄₀O₁₄₀]·60H₂O with NiCl₂·6H₂O and Ln(NO₃)₃·xH₂O at pH≈4.5. The crystal structures of (NH₄)₂₁[Gd(H₂O)₅{Ni(H₂O)}₂As₄W₄₀O₁₄₀]·51H₂O was determined by X-ray diffraction analysis and element analysis. The compound crystallizes in the monoclinic space group P2₁/n with a=19.754(3), b=24.298(4), c=39.350(6) Å, β=100.612(3)°, V=18564(5) ų, Z=2, R1(wR₂)=0.0544(0.0691). The central site S1 and two opposite sites S2 of the big cyclic ligand [As₄W₄₀O₁₄₀]²⁸⁻ are occupied by one Ln³⁺and two Ni²⁺, respectively, each site supply four O_d coordinating to metal ion, another one water molecule and other five water molecules coordinate, respectively, to Ni²⁺and Ln³⁺. Polyanion [Ln(H₂O)₅{Ni(H₂O)}₂As₄W₄₀O₁₄₀]²¹⁻ has C_2v symmetry. IR and UV–vis spectra of [NaAs₄W₄₀O₁₄₀]²⁷⁻ of the title compounds are discussed.     

Tautomeric properties, conformations and structure of N-(2-hydroxy-5-chlorophenyl) salicylaldimine

The crystal structure of N-(2-hydroxy-5-chlorophenyl) salicylaldimine (C₁₃H₁₀NO₂Cl) was determined by X-ray analysis. It crystallizes orthorhombic space group P2₁2₁2₁ with a=12.967(2) Å, b=14.438(3) Å, c=6.231(3) Å, V=1166.5(6) Å³, Z=4, D_c=1.41 g cm⁻³ and μ(MoK)=0.315 mm⁻¹. The title compound is thermochromic and the molecule is nearly planar. Both tautomeric forms (keto and enol forms in 68(3) and 32(3)%, respectively) are present in the solid state. The molecules contain strong intramolecular hydrogen bonds, N1–H1O1/O2 (2.515(1) and 2.581(2) Å) for the keto form and O1–H01N1 for the enol one. There is also strong intermolecular O2–HO1 hydrogen bonding (2.599(2) Å) between neighbouring molecules. Minimum energy conformations AM1 were calculated as a function of the three torsion angles, θ₁(N1–C7–C6–C5), θ₂(C8–N1–C7–C6) and θ₃(C9–C8–N1–C7), varied every 10°. Although the molecule is nearly planar, the AM1 optimized geometry of the title compound is not planar. The non-planar conformation of the title compound corresponding to the optimized X-ray structure is the most stable conformation in all calculations.     

Molecular structure of 4,4′-sulfandiyl-bis-thiophenol from electron diffraction

The molecular structure of 4,4′-sulfanidyl-bis-thiophenol (C₁₂H₁₀S₃) has been determined by gas electron diffraction. Assuming identical geometry and D_2h local symmetry for ---SC₆H₄S--- moieties, the following bond lengths (r_g) and bond angles were obtained: C---H = 1.101 ± 0.005, S---H = 1.388 ± 0.019, (C---C)_mean = 1.400 ± 0.003, (S---C)_mean = 1.778 ± 0.004 Å, C_ar---S---C_ar = 103.5 ± 1.3, C---C(S)---C = 120.4 ± 0.3, C(H)---C(H)---H = 119.1 ± 0.9 and C---S---H = 94.6 ± 3.1°. Two ratational forms were found to reproduce the experimental data, characterized by dihedral angles of the benzene rings with respect to the C_arSC_ar plane; ₁ = 67.8 ± 2.0°, ₂ = 4.5 ± 7.2°, and ₁ = 69.4 ± 2.0δ, ₂ = −26.6 ± 7.1°. Identical signs of ₁ and ₂ indicate that the two benzene rings are rotated in the same direction about the respective S_central---C axes.     

Influence of electronic and steric effects on stability constants and electrochemical reversibility of divalent ion complexes with glycine and sarcosine. A glass electrode potentiometric, sampled direct current polarographic, virtual potentiometric, and molecular modelling study

Cd^II complexes with glycine (gly) and sarcosine (sar) were studied by glass electrode potentiometry, direct current polarography, virtual potentiometry, and molecular modelling. The electrochemically reversible Cd^II–glycine–OH labile system was best described by a model consisting of M(HL), ML, ML₂, ML₃, ML(OH) and ML₂(OH) (M = Cd^II, L = gly) with the overall stability constants, as log β, determined to be 10.30 ± 0.05, 4.21 ± 0.03, 7.30 ± 0.05, 9.84 ± 0.04, 8.9 ± 0.1, and 10.75 ± 0.10, respectively. In case of the electrochemically quasi-reversible Cd^II–sarcosine–OH labile system, only ML, ML₂ and ML₃ (M = Cd^II, L = sar) were found and their stability constants, as log β, were determined to be 3.80 ± 0.03, 6.91 ± 0.07, and 8.9 ± 0.4, respectively. Stability constants for the ML complexes, the prime focus of this work, were thus established with an uncertainty smaller than 0.05 log units. The observed departure from electrochemical reversibility for the Cd–sarcosine–OH system was attributed mainly to the decrease in the transfer coefficient . The MM2 force field, supplemented by additional parameters, reproduced the reported crystal structures of diaqua-bis(glycinato-O,N)nickel(II) and fac-tri(glycinato)-nickelate(II) very well. These parameters were used to predict structures of all possible isomers of (i) [Ni(H₂O)₄(gly)]⁺ and [Ni(H₂O)₄(sar)]⁺; and (ii) [Ni(H₂O)₃(IDA)] and [Ni(H₂O)₃(MIDA)] (IDA = iminodiacetic acid, MIDA = N-methyl iminodiacetic acid) by molecular mechanics/simulated annealing methods. The change in strain energy, ΔU_str, that accompanies the substitution of one ligand by another (ML + L′ → ML′ + L), was computed and a strain energy ΔU_str = +0.28 kcal mol⁻¹ for the reaction [Ni(H₂O)₄(gly)]⁺ + sar → [Ni(H₂O)₄(sar)]⁺ + gly was found. This predicts the monoglycine complex to be marginally more stable. By contrast, for the reaction [Ni(H₂O)₃IDA] + MIDA → [Ni(H₂O)₃MIDA] + IDA, ΔU_str = −0.64 kcal mol⁻¹, and the monoMIDA complex is predicted to be more stable. This correlates well with (i) stability constants for Cd–gly and Cd–sar reported here; and (ii) known stability constants of ML complex for glycine, sarcosine, IDA, and MIDA.