Pyrazine-Coordinated Dinuclear and Mononuclear Ruthenium Complexes Formed via the Conversion of the Triply Chlorido-Bridged Diruthenium(II) Complex.

The pyrazine-coordinated dinuclear and mononuclear ruthenium complexes were synthesized through the framework conversion reactions of the triply chlorido-bridged diruthenium(II) complex [{RuII,II(bbpma)}2(µ-Cl)3]+ (bbpma; benzylbis(2-pyridylmethyl)amine, [1]+) in the presence of pyrazine, which could function as the simple molecular multinucleation ligand of metal compounds. A reduction reaction of fac-[RuIIICl3(bbpma)] with zinc in the presence of hydrochloric acid afforded [1]+ in solution, and the following addition of pyrazine (1 equiv) in the solution led to the formation of a singly pyrazine (pz)-bridged diruthenium complex, [{RuII,II(µ-Cl2ZnCl2)(bbpma)}2(µ-pz)] ([2(II,II)(ZnCl2)2]). The stoichiometric two-electron oxidation of [2(II,II)(ZnCl2)2] was successfully proceeded, and a Ru(III)-Ru(III) species, [{RuIII,IIICl2(bbpma)}2(µ-pz)](PF6)2 ([III,III](PF6)2), was isolated. The reaction of [1]+ with excess amounts of pyrazine without hydrochloric acid afforded mononuclear Ru(III) and Ru(II) complexes containing one or two pyrazine, fac-[RuClm(pz)3-m(bbpma)]+ (m = 2; [3]+; m = 1; [4]+). The details of the electrochemical and spectroscopic properties of [1]+-[4]+ in organic and aqueous solutions were discussed.

Ru(IV)-Ru(IV) complexes having the doubly oxido-bridged core with a bridging carbonato or hydrogencarbonato ligand.

Ru(IV)-Ru(IV) complexes having the doubly oxido-bridged diamond core with a bridging carbonato or hydrogencarbonato ligand, [{RuIV(ebpma)}2(µ-O)2(µ-O2CO(H)m)]Xn (ebpma; ethylbis(2-pyridylmethyl)amine, m = 0; [IV,IV]X2 (X = PF6, ClO4), m = 1; [IV,IV_1H](ClO4)3), were isolated via the oxidation of the corresponding carbonato-bridged Ru(III)-Ru(IV) complex ([III,IV]+), and "[IV,IV](ClO4)2 and [IV,IV_1H](ClO4)3" were structurally characterized. The electrochemical and spectroscopic properties of [IV,IV]2+ and [IV,IV_1H]3+ were investigated both in organic solvents and aqueous solutions. The reactivity toward organic solvents having (a) methyl group(s) and reactions with organic substrates were studied as well. This should be the first time when systematic comparisons of the Ru(IV)-Ru(IV) species and corresponding Ru(III)-Ru(IV) complexes in the same tridentate ligand system were made.

Synthesis of Carbonato- and Doubly Oxido-Bridged Diruthenium(III,IV) Complex and Reactions with Cations.

Doubly oxido-bridged transition metal moieties, {M2(µ-O)2}, play important roles as oxidation reaction centers in nature. This work features a diruthenium(III,IV) complex with a doubly oxido-bridged core {Ru2III,IV(µ-O)2}3+ with a carbonato bridged between the two ruthenium centers, M[{RuIII,IV(ebpma)}2(µ-O)2(µ-O2CO)]2(PF6)3 (M[1CO3]2(PF6)3; Carbonato complex, ebpma; ethylbis(2-pyridymethyl)amine), and explores the interactions of this complex with cations (H+ and M+). M[1CO3]2(PF6)3 was formed via reactions of a singly oxido-bridged complex, [{RuIII,IVCl2(ebpma)}2(µ-O)]PF6·(CH3)2CO, with M2CO3 (M = K, Na) or with CO2(g), adjusted to around pH 12 with NaOH(aq.), in a water-acetone mixed solvent. The Carbonato complex was isolated as a powder in the form of M[1CO3]2(PF6)3 (M = K, Na), because of the interactions between the carbonato moiety and K+ or Na+ in the solid structure. In acidic aqueous solutions, unexpectedly, the carbonato ligand remained bound to the doubly bridged core, {Ru2III,IV(µ-O)2}3+ or {Ru2III,IV(µ-O)(µ-OH)}4+, without decarboxylation even under pH 1.0. Two-step one-protonation/deprotonation occurred reversibly between pH 1.0 and 13.2 to the bridging oxido and carbonato ligands. The structures of the corresponding one- and two-protonated complexes ([1CO3H]2+ and [1CO32H]3+) were successfully characterized.

N-C bond formation between two anilines coordinated to a ruthenium center in cis-form affording a 3,5-cyclohexadiene-1,2-diimine moiety.

Ruthenium complexes containing two anilines or its derivatives, cis-[RuII(NH2C6H5)2(bpy)2]2+ ([1]2+) and cis-[RuII(NH2C6H4(4-CH3))2(bpy)2]2+ ([2]2+), were oxidized by four molar equivalents of (NH4)4[CeIV(SO4)4]·2H2O to give N 1-phenylcyclohexa-3,5-diene-1,2-diimineruthenium(ii) complexes, cis-[RuII(NHC6H4 NC6H5)(bpy)2]2+ ([4]2+) and cis-[RuII(NHC6H3(4-CH3)NC6H4(4-CH3))(bpy)2]2+ ([5]2+), respectively, through an N-C bond formation between two aniline ligands cis-coordinated to the ruthenium center.

Framework Conversion of Oxido-Bridged Dinuclear Ruthenium Complexes.

Syntheses, properties, and reactions of hydroxido- or oxido-bridged dinuclear ruthenium complexes bearing a tridentate auxiliary ligand, ethylbis(2-pyridylmethyl)amine (ebpma) or benzylbis(2-pyridylmethyl)amine (bbpma), have been investigated. Reduction reactions of a singly oxido-bridged diruthenium complex bearing ebpma, [{RuIII,IVCl2(ebpma)}2(µ-O)]+ ([2Cl]+), by zinc in acetonitrile afforded an acetonitrile-substituted singly oxido-bridged complex in the RuIII-RuIII isovalent state, [{RuIII,IIICl(NCCH3)(ebpma)}2(µ-O)]2+ ([2CH3CN]2+). Chlorido ligand abstraction reactions using silver salts have also been attempted. Through a reaction of [2Cl]+ with two equimolar amounts of AgNO3 in water-acetone, a singly oxido-bridged complex having an aqua and a hydroxido, [{RuIIICl(OH2)(ebpma)}(µ-O){RuIVCl(OH)(ebpma)}]2+ ([2H2O-OH]2+), was obtained. Reactions with four equimolar amounts of AgL (L = CH3COO- or NO3-) in water-acetone gave doubly oxido- and bidentate oxygen donor ligand-bridged diruthenium complexes of Ru(III)-Ru(IV), [{RuIII,IV(ebpma)}2(µ-O)2(µ-L)]2+ ([3L]2+; L = O2CCH3; [3CH3COO]2+, L = O2NO; [3NO3]2+). Reactions of [3L]2+ under acidic conditions afforded a corresponding one-protonated species having the {Ru2(µ-O)(µ-OH)} core. Reactivity and electronic structure of the oxido-bridged diruthenium complexes were studied by electrochemical, spectroscopic, and theoretical methods.

Nitrosylruthenium Complexes as Polymerization Catalysts for Acrylonitrile in DMF.

Nitrosylruthenium complexes bearing two 2,2'-bipyridine (bpy) or 2-pyridinecarboxylate (pyc) ligands, [Ru(NO)X(bpy)2 ]3+ (X=CH3 CN, CH2 =CHCN, H2 O, Cl, ONO2 ) and [Ru(NO)(OH2 )(pyc)2 ]+ , were used as catalysts for the polymerization of acrylonitrile in N,N-dimethylformamide (DMF) under air without initiators to obtain polyacrylonitrile (PAN) with a high molecular weight and a narrow molecular weight distribution.

Acetylacetonato-based pincer-type nickel(ii) complexes: synthesis and catalysis in cross-couplings of aryl chlorides with aryl Grignard reagents.

In this work, three different types of acetylacetonato-based pincer-type nickel(ii) complexes (2) were prepared. Complex 2a possessed the tridentate ONN ligand, which was constructed by the condensation reaction of acetylacetone with N,N-diethylethylenediamine. Complex 2b contained the PPh2 donor group in contrast to the NEt2 group in 2a, i.e., an ONP ligand framework. Complex 2c was composed of the NNN ligand, which was prepared by the reaction of 4-((2,4,6-trimethylphenyl)amino)pent-3-en-2-one with N,N-diethylethylenediamine. In addition to X-ray diffraction analysis, these complexes were characterized spectroscopically. Their catalytic activity for a cross-coupling reaction of aryl halides with aryl Grignard reagents was also evaluated. Among these complexes, 2b acted as an effective catalyst for the cross-coupling reaction using aryl chlorides as electrophiles. The electronic properties of these Ni(ii) complexes were investigated by cyclic voltammetry and density functional theory calculations.

Dinuclear Ruthenium(III)-Ruthenium(IV) Complexes, Having a Doubly Oxido-Bridged and Acetato- or Nitrato-Capped Framework.

Dinuclear ruthenium complexes in a mixed-valence state of Ru(III)-Ru(IV), having a doubly oxido-bridged and acetato- or nitrato-capped framework, [{Ru(III,IV)(ebpma)}2(µ-O)2(µ-L)](PF6)2 [ebpma = ethylbis(2-pyridylmethyl)amine; L = CH3COO(-) (1), NO3(-) (2)], were synthesized. In aqueous solutions, the diruthenium complex 1 showed multiple redox processes accompanied by proton transfers depending on the pH. The protonated complex of 1, which is described as 1H+, was obtained.

Formation of bis(2-pyridylcarbonyl)aminate by oxidation of ethylbis(2-pyridylmethyl)amine on the trichloridoruthenium(III) complex.

Oxidation of the facial-type trichloridoruthenium(III) complex bearing ethylbis(2-pyridyl-methyl)amine (ebpma), fac-[Ru(III)Cl3(ebpma)], with an equimolecular amount of (NH4)2[Ce(IV)(NO3)6] in acetonitrile afforded a ligand-based oxidation product of an acetonitriledichloridoruthenium(III) complex having bis(2-pyridylcarbonyl)aminato (bpca), [Ru(III)Cl2(NCCH3)(bpca)]. The complex changed into a trichloridoruthenium(III) complex by a reaction with hydrochloric acid and the triacetonitrileruthenium(II) complex by reduction with Zn in ethanol-acetonitrile. The bpca moiety showed interactions with cations such as protons.

Synthesis and characterization of ethylbis(2-pyridylethyl)amineruthenium complexes and two different types of C-H bond cleavage at an ethylene arm.

Ruthenium complexes bearing ethylbis(2-pyridylethyl)amine (ebpea), which has flexible -C(2)H(4)- arms between the amine and the pyridyl groups and coordinates to a metal center in facial and meridional modes, have been synthesized and characterized. Three trichloro complexes, fac-[Ru(III)Cl(3)(ebpea)] (fac-[1]), mer-[Ru(III)Cl(3)(ebpea)] (mer-[1]), and mer-[Ru(II)Cl(3){η(2)-N(C(2)H(5))(C(2)H(4)py)═CH-CH(2)py}] (mer-[2]), were synthesized using the Ru blue solution. Formation of mer-[2] proceeded via a C-H activation of the CH(2) group next to the amine nitrogen atom of the ethylene arm. Reduction reactions of fac- and mer-[1] afforded a triacetonitrile complex mer-[Ru(II)(CH(3)CN)(3)(ebpea)](PF(6))(2) (mer-[3](PF(6))(2)). Five nitrosyl complexes fac-[RuX(2)(NO)(ebpea)]PF(6) (X = Cl for fac-[4]PF(6); X = ONO(2) for fac-[5]PF(6)) and mer-[RuXY(NO)(ebpea)]PF(6) (X = Cl, Y = Cl for mer-[4]PF(6); X = Cl, Y = CH(3)O for mer-[6]PF(6); X = Cl, Y = OH for mer-[7]PF(6)) were synthesized and characterized by X-ray crystallography. A reaction of mer-[2] in H(2)O-C(2)H(5)OH at room temperature afforded mer-[1]. Oxidation of C(2)H(5)OH in H(2)O-C(2)H(5)OH and i-C(3)H(7)OH in H(2)O-i-C(3)H(7)OH to acetaldehyde and acetone by mer-[2] under stirring at room temperature occurred with formation of mer-[1]. Alternative C-H activation of the CH(2) group occurred next to the pyridyl group, and formation of a C-N bond between the CH moiety and the nitrosyl ligand afforded a nitroso complex [Ru(II)(N(3))(2){N(O)CH(py)CH(2)N(C(2)H(5))C(2)H(4)py}] ([8]) in reactions of nitrosyl complexes with sodium azide in methanol, and reaction of [8] with hydrochloric acid afforded a corresponding chloronitroso complex [Ru(II)Cl(2){N(O)CH(py)CH(2)N(C(2)H(5))C(2)H(4)py}] ([9]).

A mixed-valence diruthenium complex, triply bridged by mixed-moieties of chloro and methoxo ligands.

A mixed-valence diruthenium complex, whose metal centres were triply bridged by one chloro and two methoxo ligands, was synthesized and characterized by X-ray structural analysis, electrochemistry and spectroscopy, and its mixed-valence state was classified into Class III.

Reactions of ruthenium complexes having pyridyl-containing ligands, 2-pyridinecarboxylato and 2,2'-bipyridine, with an azide ion: formation of nitrido-bridged diruthenium complexes.

Reactions of ruthenium complexes having 2-pyridinecarboxylato and 2,2'-bipyridine ligands with sodium azide in alcohol afforded nitrido-bridged diruthenium complexes, [{Ru(OR)(pyca)(bpy)}2(mu-N)](+) (R = CH3, C2H5). Diruthenium complexes showed diamagnetic properties, a linear Ru-N-Ru coordination configuration, and two irreversible oxidation waves and two reversible reduction waves.

Synthesis of nitrosylruthenium complexes containing 2,2':6',2"-terpyridine by reactions of alkoxo complexes with acids.

Nitrosylruthenium complexes containing 2,2':6',2"-terpyridine (terpy) have been synthesized and characterized. The three alkoxo complexes trans-(NO, OCH3), cis-(Cl, OCH3)-[RuCl(OCH3)(NO)(terpy)]PF6 ([2]PF6), trans-(NO, OC2H5), cis-(Cl, OC2H5)-[RuCl(OC2H5)(NO)(terpy)]PF6 ([3]PF6), and [RuCl(OC3H7)(NO)(terpy)]PF6 ([4]PF6) were synthesized by reactions of trans-(Cl, Cl), cis-(NO, Cl)-[RuCl2(NO)(terpy)]PF6 ([1]PF6) with NaOCH3 in CH3OH, C2H5OH, and C3H7OH, respectively. Reactions of [3]PF6 with an acid such as hydrochloric acid and trifluoromethansulforic acid afford nitrosyl complexes in which the alkoxo ligand is substituted. The geometrical isomer of [1]PF6, trans-(NO, Cl), cis-(Cl, Cl)-[RuCl2(NO)(terpy)]PF6 ([5]PF6), was obtained by the reaction of [3]PF6 in a hydrochloric acid solution. Reaction of [3]PF6 with trifluoromethansulforic acid in CH3CN gave trans-(NO, Cl), cis-(CH3CN, Cl)-[RuCl(CH3CN)(NO)(terpy)]2+ ([6]2+) under refluxing conditions. The structures of [3]PF6, [4]PF6.CH3CN, [5]CF3SO3, and [6](PF6)2 were determined by X-ray crystallograpy.

Concerted proton-electron transfer in the oxidation of hydrogen-bonded phenols.

Three phenols with pendant, hydrogen-bonded bases (HOAr-B) have been oxidized in MeCN with various one-electron oxidants. The bases are a primary amine (-CPh(2)NH(2)), an imidazole, and a pyridine. The product of chemical and quasi-reversible electrochemical oxidations in each case is the phenoxyl radical in which the phenolic proton has transferred to the base, (*)OAr-BH(+), a proton-coupled electron transfer (PCET) process. The redox potentials for these oxidations are lower than for other phenols, predominately from the driving force for proton movement. One-electron oxidation of the phenols occurs by a concerted proton-electron transfer (CPET) mechanism, based on thermochemical arguments, isotope effects, and DeltaDeltaG(++)/DeltaDeltaG degrees . The data rule out stepwise paths involving initial electron transfer to form the phenol radical cations [(*)(+)HOAr-B] or initial proton transfer to give the zwitterions [(-)OAr-BH(+)]. The rate constant for heterogeneous electron transfer from HOAr-NH(2) to a platinum electrode has been derived from electrochemical measurements. For oxidations of HOAr-NH(2), the dependence of the solution rate constants on driving force, on temperature, and on the nature of the oxidant, and the correspondence between the homogeneous and heterogeneous rate constants, are all consistent with the application of adiabatic Marcus theory. The CPET reorganization energies, lambda = 23-56 kcal mol(-)(1), are large in comparison with those for electron transfer reactions of aromatic compounds. The reactions are not highly non-adiabatic, based on minimum values of H(rp) derived from the temperature dependence of the rate constants. These are among the first detailed analyses of CPET reactions where the proton and electron move to different sites.

Regulation of geometry around the ruthenium center of bis(2-pyridinecarboxylato) complexes by the nitrosyl moiety: syntheses, structures, and theoretical studies.

cis-[Ru(NO)Cl(pyca)(2)] (pyca = 2-pyridinecarboxylato), in which the two pyridyl nitrogen atoms of the two pyca ligands coordinate at the trans position to each other and the two carboxylic oxygen atoms at the trans position to the nitrosyl ligand and the chloro ligand, respectively (type I shown as in Chart 1), reacted with NaOCH(3) to generate cis-[Ru(NO)(OCH(3))(pyca)(2)] (type I). The geometry of this complex was confirmed to be the same as the starting complex by X-ray crystallography: C(13.5)H(13)N(3)O(6.5)Ru; monoclinic, P2(1)/n; a = 8.120(1), b = 16.650(1), c = 11.510(1) A; beta = 99.07(1) degrees; V = 1536.7(2) A(3); Z = 4. The cis-trans geometrical change reaction occurred in the reactions of cis-[Ru(NO)(OCH(3))(pyca)(2)] (type I) in water and alcohol (ROH, R = CH(3), C(2)H(5)) to form [[trans-Ru(NO)(pyca)(2)](2)(H(3)O(2))](+) (type V) and trans-[Ru(NO)(OR)(pyca)(2)] (type V). The reactions of the trans-form complexes, trans-[Ru(NO)(H(2)O)(pyca)(2)](+) (type V) and trans-[Ru(NO)(OCH(3))(pyca)(2)] (type V), with Cl(-) in hydrochloric acid solution afforded the cis-form complex, cis-[Ru(NO)Cl(pyca)(2)] (type I). The favorable geometry of [Ru(NO)X(pyca)(2)](n)(+) depended on the nature of the coexisting ligand X. This conclusion was confirmed by theoretical, synthetic, and structural studies. The mono-pyca-containing nitrosylruthenium complex (C(2)H(5))(4)N[Ru(NO)Cl(3)(pyca)] was synthesized by the reaction of [Ru(NO)Cl(5)](2)(-) with Hpyca and characterized by X-ray structural analysis: C(14)H(24)N(3)O(3)Cl(3)Ru; triclinic, Ponemacr;, a = 7.631(1), b = 9.669(1), c = 13.627(1) A; alpha = 83.05(2), beta = 82.23(1), gamma = 81.94(1) degrees; V = 981.1(1) A(3); Z = 2. The type II complex of cis-[Ru(NO)Cl(pyca)(2)] was synthesized by the reaction of [Ru(NO)Cl(3)(pyca)](-) or [Ru(NO)Cl(5)](2)(-) with Hpyca and isolated by column chromatography. The structure was determined by X-ray structural analysis: C(12)H(8)N(3)O(5)ClRu; monoclinic, P2(1)/n; a = 10.010(1), b = 13.280(1), c = 11.335(1) A; beta = 113.45(1) degrees; V = 1382.4(2) A(3); Z = 4.

Reactions of acetonitrile coordinated to a nitrosylruthenium complex with H2O or CH(3)OH under mild conditions: structural characterization of imido-type complexes.

The reaction of cis-[Ru(NO)(CH(3)CN)(bpy)(2)](3+) (bpy = 2,2'-bipyridine) in H(2)O at room temperature proceeded to afford two new nitrosylruthenium complexes. These complexes have been identified as nitrosylruthenium complexes containing the N-bound methylcarboxyimidato ligand, cis-[Ru(NO)(NH=C(O)CH(3))(bpy)(2)](2+), and methylcarboxyimido acid ligand, cis-[Ru(NO)(NH=C(OH)CH(3))(bpy)(2)](3+), formed by an electrophilic reaction at the nitrile carbon of the acetonitrile coordinated to the ruthenium ion. The X-ray structure analysis on a single crystal obtained from CH(3)CN-H(2)O solution of cis-[Ru(NO)(NH=C(O)CH(3))(bpy)(2)](PF(6))(3) has been performed: C(22)H(20.5)N(6)O(2)P(2.5)F(15)Ru, orthorhombic, Pccn, a = 15.966(1) A, b = 31.839(1) A, c = 11.707(1) A, V = 5950.8(4) A(3), and Z = 8. The structural results revealed that the single crystal consisted of 1:1 mixture of cis-[Ru(NO)(NH=C(O)CH(3))(bpy)(2)](2+) and cis-[Ru(NO)(NH=C(OH)CH(3))(bpy)(2)](3+) and the structural formula of this single crystal was thus [Ru(NO)(NH=C(OH(0.5))CH(3))(bpy)(2)](PF(6))(2.5). The reaction of cis-[Ru(NO)(CH(3)CN)(bpy)(2)](3+) in dry CH(3)OH-CH(3)CN at room temperature afforded a nitrosylruthenium complex containing the methyl methylcarboxyimidate ligand, cis-[Ru(NO)(NH=C(OCH(3))CH(3))(bpy)(2)](3+). The structure has been determined by X-ray structure analysis: C(25)H(29)N(8)O(18)Cl(3)Ru, monoclinic, P2(1)/c, a = 13.129(1) A, b = 17.053(1) A, c = 15.711(1) A, beta = 90.876(5) degrees, V = 3517.3(4) A(3), and Z = 4.

Structural and Electrochemical Comparison of Copper(II) Complexes with Tripodal Ligands.

A series of copper(II) complexes with tripodal polypyridylmethylamine ligands, such as tris(2-pyridylmethyl)amine (tpa), ((6-methyl-2-pyridyl)methyl)bis(2-pyridylmethyl)amine (Me(1)tpa), bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)amine (Me(2)tpa), and tris((6-methyl-2-pyridyl)methyl)amine (Me(3)tpa), have been synthesized and characterized by X-ray crystallography. [Cu(H(2)O)(tpa)](ClO(4))(2) (1) crystallized in the monoclinic system, space group P2(1)/a, with a = 15.029(7) Å, b = 9.268(2) Å, c = 17.948(5) Å, beta = 113.80(3) degrees, and Z = 4 (R = 0.061, R(w) = 0.059). [CuCl(Me(1)tpa)]ClO(4) (2) crystallized in the triclinic system, space group P&onemacr;, with a = 13.617(4) Å, b = 14.532(4) Å, c = 12.357(4) Å, alpha = 106.01(3) degrees, beta = 111.96(2) degrees, gamma = 71.61(2) degrees, and Z = 4 (R = 0.054, R(w) = 0.037). [CuCl(Me(2)tpa)]ClO(4) (3) crystallized in the monoclinic system, space group P2(1)/n, with a = 19.650(4) Å, b = 13.528(4) Å, c = 8.55(1) Å, beta = 101.51(5) degrees, and Z = 4 (R = 0.071, R(w) = 0.050). [CuCl(Me(3)tpa)][CuCl(2)(Me(3)tpa)]ClO(4) (4) crystallized in the monoclinic system, space group P2(1)/a, with a = 15.698(6) Å, b = 14.687(7) Å, c = 19.475(4) Å, beta = 97.13(2) degrees, and Z = 4 (R = 0.054, R(w) = 0.038). All the Cu atoms of 1-4 have pentacoordinate geometries with three pyridyl and one tertiary amino nitrogen atoms, and a chloride or aqua oxygen atom. Nitrite ion coordinated to the Cu(II) center of Me(1)tpa, Me(2)tpa, and Me(3)tpa complexes with only oxygen atom to form nitrito adducts. The cyclic voltammograms of [Cu(H(2)O)(Me(n)()tpa)](2+) (n = 0, 1, 2, and 3) in the presence of NO(2)(-) in H(2)O (pH 7.0) revealed that the catalytic activity for the reduction of NO(2)(-) increases in the order Me(3)tpa << Me(2)tpa << Me(1)tpa < tpa complexes.