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David N. Hendrickson

Publications and source records attributed to David N. Hendrickson.

11 recordsLinked to original sources
PubMed1999

High-Field EPR Study of Resonance-Delocalized [Fe(2)(OH)(3)(tmtacn)(2)](2+).

High-frequency EPR data are reported for the Fe(II/III) valence delocalized dinuclear complex [Fe(2)(OH)(3)(tmtacn)(2)](2+). A full-matrix diagonalization approach is used to derive the spin-Hamiltonian parameters for this S(T) = (9)/(2) complex. At high fields (up to 14.5 T) and high frequencies (189-433 GHz) fine structure peaks due to resonances between the Kramers doublets (M(s) = (9)/(2), (7)/(2),.) are observed. The spacing of the fine structure reveals that the axial zero-field splitting (ZFS) parameter D is +1.08(1) cm(-)(1); a very small rhombic ZFS (|E| </= 0.01 cm(-)(1)) is suggested by line broadening of these interdoublet resonances. Simulations reveal that g is close to 2.00, and very nearly isotropic: g(x)() = g(y)() = g(z)() = 2.00(2). This complex is a model for the valence-delocalized [Fe(2)S(2)](+) pairs found in larger iron-sulfur clusters, such as the cofactors from the nitrogenase system. This work indicates that HFEPR is a viable technique for the study of high-spin centers in proteins.

Journal Article↗
PubMed1998

Dinuclear and Hexanuclear Iron(III) Oxide Complexes with a Bis(bipyridine) Ligand: A New [Fe(6)(&mgr;(3)-O)(4)](10+) Core.

The use of the bis(bipyridine) ligand L (1,2-bis(2,2'-bipyridyl-6-yl)ethane) has yielded new dinuclear and hexanuclear complexes. The FeCl(3)/NaO(2)CPh/L (4:4:1) reaction system in MeCN gives red-brown [Fe(6)O(4)Cl(4)(O(2)CPh)(4)L(2)][FeCl(4)](2) (1). The same reaction system in a 3:3:1 ratio in MeOH gives orange [Fe(2)(OMe)(2)Cl(2)(O(2)CPh)L][FeCl(4)] (2). Complex 1.2MeCN: monoclinic, P2(1)/a, a = 15.317(2) Å, b = 18.303(3) Å, c = 16.168(3) Å, beta = 108.91(1) degrees, and Z = 2. Complex 2: triclinic, P&onemacr;, a = 14.099(6) Å, b = 18.510(7) Å, c = 7.108(3) Å, alpha = 96.77(2) degrees, beta = 99.45(2) degrees, gamma = 81.16(2) degrees, and Z = 2. The cation of 1 consists of a near-planar [Fe(6)(&mgr;(3)-O)(4)](10+) core that can be described as three edge-fused [Fe(2)O(2)] rhombs to which are attached two additional Fe atoms. The cation of 2 contains a [Fe(2)(&mgr;-OMe)(2)(&mgr;-O(2)CPh)](3+) core. In both cations, the L group acts as a bridging ligand across an Fe(2) unit, with the bpy rings essentially parallel. Variable-temperature solid-state magnetic-susceptibility studies of 1 and 2 in the 2.00-300 K range reveal that for both complexes the data are consistent with an S = 0 cation and S = (5)/(2) [FeCl(4)](-) anions. These conclusions were confirmed by magnetization vs field studies in the 2.00-4.00 K and 10.0-50.0 kG ranges. Fitting of the data for 2 to the appropriate theoretical equation for an equimolar composition of Fe(2) cations and [FeCl(4)](-) anions allowed the exchange interaction in the cation to be determined as J = -10.5 cm(-)(1) (H = -2JS(1)S(2)) with g held at 2.00. The obtained J value is consistent with that predicted by a previously published magnetostructural relationship.

Journal Article↗
PubMed1998

Structural and Magnetochemical Properties of Mono-, Di-, and Trinuclear Manganese(III) Dithiolate Complexes.

Aerial oxidation of Mn(II)/ptt(3)(-) (ptt(3)(-) = propane-1,2,3-trithiolate) mixtures gives [Mn(2)(pttd)(2)](2)(-), where pttd(4)(-) is the mono(disulfide) of ptt(3)(-). (NEt(3)Bz)(2)[Mn(2)(pttd)(2)] (2) crystallizes in space group P2(1)/c with (at -158 degrees C) a = 11.540(2) Å, b = 12.115(2) Å, c = 17.478(4) Å, beta = 101.78(1) degrees, and Z = 2. The anion contains a doubly-bridged [Mn(2)S(8)] core (Mn.Mn = 3.598(2) Å) with five-coordinate Mn(III) ions, very similar to previously reported [Mn(2)(edt)(4)](2)(-) (anion of 1; edt(2)(-) = ethane-1,2-dithiolate). Aerial oxidation of Mn(II)/pdt(2)(-) (pdt(2)(-) = propane-1,3-dithiolate) mixtures gives [Mn(3)(pdt)(5)](2)(-), which is mixed valent (Mn(II), 2Mn(III)). (PPh(4))(2)[Mn(3)(pdt)(5)] (3) crystallizes in space group P&onemacr; with (at -161 degrees C) a = 14.385(6) Å, b = 23.734(11) Å, and Z = 2. The anion contains a near-linear Mn(III)Mn(II)Mn(III) unit with five-coordinate Mn(III), six-coordinate Mn(II), and three thiolate bridges between each Mn(2) pair; Mn.Mn separations are 3.123(3) and 3.101(3) Å. Aerial oxidation of Mn(II)/edt(2)(-)/ImH (ImH = imidazole) mixtures gives [Mn(edt)(2)(ImH)](-). (NEt(4))[Mn(edt)(2)(ImH)] (4) crystallizes in space group P2(1)/n with (at -72 degrees C) a = 13.974(5) Å, b = 14.317(5) Å, c = 10.564(3) Å, beta = 90.13(2) degrees, and Z = 4. The anion is five-coordinate and square-pyramidal. Aerial oxidation of Mn(II)/edt(2)(-)/Im(-) mixtures gave [Mn(2)(Im)(edt)(4)](3)(-), which contains two Mn(III) ions. (NMe(4))(3)[Mn(2)(Im)(edt)(4)] (5) crystallizes in space group Pna2(1) with (at -160 degrees C) a = 17.965(5) Å, b = 16.094(4) Å, c = 14.789(3) Å, and Z = 4. The five-coordinate Mn(III) ions are bridged by the Im(-) group across a Mn.Mn separation of 6.487(2) Å. The anion of 4 contains high-spin Mn(III) (S = 2) and exhibits inter-anion antiferromagnetic exchange interactions (J = -0.15 cm(-)(1), g = 1.91) propagated by interanion NH.S hydrogen bonds. Complexes 1-3 and 5 all possess intraanion antiferromagnetic exchange interactions; the fitting parameters are as follows: 1, J = -19.0 cm(-)(1), g = 1.96, D = -0.22 cm(-)(1); 2, J = -16.4 cm(-)(1), g = 1.96, D = -0.22 cm(-)(1); 3, J = -18.8 cm(-)(1), g = 2.00; 5, J = -1.75 cm(-)(1), g = 1.84, D = -0.028 cm(-)(1) (H = -2JS(i)()S(j)() convention). Complexes 1, 2, and 5 have S = 0 ground states, while that of 3 is S = (3)/(2).

Journal Article↗
PubMed1997

Electron Transfer in Mixed-Valence [Fe(III)(2)Fe(II)O(O(2)CCH(3))(6)(3-Cl-py)(3)].3-Cl-py: Effects of a Crystallographic Phase Transition and Conversion of Solvate and Ligand Molecules from Statically Disordered to Dynamically Disordered on the Valence Detrapping.

A crystallographic phase transition involving changes in the solvate molecule has been found for mixed-valence [Fe(3)O(O(2)CCH(3))(6)(3-Cl-py)(3)].3-Cl-py (1), where 3-Cl-py is 3-chloropyridine. Single-crystal X-ray structures were determined at 300, 228, 200, 169, and 122 K for complex 1. At 300, 228, and 200 K the crystal is monoclinic, space group P2(1)/c, whereas at 169 and 122 K it is triclinic, space group P&onemacr;. Determinations of the unit cell parameters at several temperatures shows that a reversible crystallographic phase transition between the monoclinic and triclinic forms occurs at approximately 200 K. Complex 1 crystallizes in the monoclinic space group P2(1)/c at 300 K, having a unit cell with a = 21.212(8) Å, b = 8.434(2) Å, c = 23.676(3) Å, and Z = 4. Refinement with 5702 observed [F(o) > 4sigma(F(o))] reflections gave R = 0.0542 and R(w) = 0.0937. Complex 1 crystallizes in the triclinic space group P&onemacr; at 122 K, having a unit cell with a = 20.983(11) Å, b = 8.360(4) Å, c = 23.293(10) Å, and Z = 4. At 300 K there is one somewhat asymmetric Fe(3)O complex in the structure. The core dimensions in the Fe(3)O complex at 300 K indicate that the complex is becoming almost valence-detrapped. At 122 K there are two different Fe(3)O complexes in the unit cell, both of which are similar in dimensions. As the temperature is decreased from 300 to 122 K, each Fe(3)O complex becomes more and more distorted in an equilateral triangle. At 122 K one iron ion in each Fe(3)O complex clearly is a high-spin Fe(II) ion and the other two are high-spin Fe(III) ions. There are significant changes in the nature of the 3-Cl-py solvate molecules above and below the phase transition that are likely important in controlling the valence detrapping. At 122 K there are two different Fe(3)O complexes, each with their nearby 3-Cl-py solvate molecules in one position. There are three different phases: a monoclinic one with all solvate molecules disordered, a second triclinic phase at 169 K with half of the solvate molecules disordered, and a third triclinic phase at 122 K with all solvate molecules statically ordered. (57)Fe Mössbauer spectra taken in the 110-293 K range show that complex 1 converts from valence-trapped at 110 K to become detrapped by 293 K, where a single quadrupole-split doublet is seen. Throughout the 140-230 K range it was necessary to employ one Fe(III) doublet and two Fe(II) doublets to fit each Mössbauer spectrum. It is shown that the two Fe(II) doublets likely arise from Fe(3)O complexes experiencing the different disordered solvate environments described above. Thus, while the approximately 200 K structural phase transition involving the solvate molecules does not precipitously lead to an increase in the rate of electron transfer in Fe(3)O complexes in 1, it is clear that the changes seen in the solvate molecules from X-ray structures do play a major role in the valence detrapping in complex 1.

Journal Article↗
PubMed1996

Tetranuclear and Octanuclear Manganese Carboxylate Clusters: Preparation and Reactivity of (NBu(n)(4))[Mn(4)O(2)(O(2)CPh)(9)(H(2)O)] and Synthesis of (NBu(n)(4))(2)[Mn(8)O(4)(O(2)CPh)(12)(Et(2)mal)(2)(H(2)O)(2)] with a "Linked-Butterfly" Structure.

The reaction of Mn(O(2)CPh)(2).2H(2)O and PhCO(2)H in EtOH/MeCN with NBu(n)(4)MnO(4) gives (NBu(n)(4))[Mn(4)O(2)(O(2)CPh)(9)(H(2)O)] (4) in high yield (85-95%). Complex 4 crystallizes in monoclinic space group P2(1)/c with the following unit cell parameters at -129 degrees C: a = 17.394(3) Å, b = 19.040(3) Å, c = 25.660(5) Å, beta = 103.51(1) degrees, V = 8262.7 Å(3), Z = 4; the structure was refined on F to R (R(w)) = 9.11% (9.26%) using 4590 unique reflections with F > 2.33sigma(F). The anion of 4 consists of a [Mn(4)(&mgr;(3)-O)(2)](8+) core with a "butterfly" disposition of four Mn(III) atoms. In addition to seven bridging PhCO(2)(-) groups, there is a chelating PhCO(2)(-) group at one "wingtip" Mn atom and terminal PhCO(2)(-) and H(2)O groups at the other. Complex 4 is an excellent steppingstone to other [Mn(4)O(2)]-containing species. Treatment of 4 with 2,2-diethylmalonate (2 equiv) leads to isolation of (NBu(n)(4))(2)[Mn(8)O(4)(O(2)CPh)(12)(Et(2)mal)(2)(H(2)O)(2)] (5) in 45% yield after recrystallization. Complex 5 is mixed-valent (2Mn(II),6Mn(III)) and contains an [Mn(8)O(4)](14+) core that consists of two [Mn(4)O(2)](7+) (Mn(II),3Mn(III)) butterfly units linked together by one of the &mgr;(3)-O(2)(-) ions in each unit bridging to one of the body Mn atoms in the other unit, and thus converting to &mgr;(4)-O(2)(-) modes. The Mn(II) ions are in wingtip positions. The Et(2)mal(2)(-) groups each bridge two wingtip Mn atoms from different butterfly units, providing additional linkage between the halves of the molecule. Complex 5.4CH(2)Cl(2) crystallizes in monoclinic space group P2(1)/c with the following unit cell parameters at -165 degrees C: a = 16.247(5) Å, b = 27.190(8) Å, c = 17.715(5) Å, beta = 113.95(1) degrees, V = 7152.0 Å(3), Z = 4; the structure was refined on F to R (R(w)) = 8.36 (8.61%) using 4133 unique reflections with F > 3sigma(F). The reaction of 4 with 2 equiv of bpy or picolinic acid (picH) yields the known complex Mn(4)O(2)(O(2)CPh)(7)(bpy)(2) (2), containing Mn(II),3Mn(III), or (NBu(n)(4))[Mn(4)O(2)(O(2)CPh)(7)(pic)(2)] (6), containing 4Mn(III). Treatment of 4 with dibenzoylmethane (dbmH, 2 equiv) gives the mono-chelate product (NBu(n)(4))[Mn(4)O(2)(O(2)CPh)(8)(dbm)] (7); ligation of a second chelate group requires treatment of 7 with Na(dbm), which yields (NBu(n)(4))[Mn(4)O(2)(O(2)CPh)(7)(dbm)(2)] (8). Complexes 7 and 8 both contain a [Mn(4)O(2)](8+) (4Mn(III)) butterfly unit. Complex 7 contains chelating dbm(-) and chelating PhCO(2)(-) at the two wingtip positions, whereas 8 contains two chelating dbm(-) groups at these positions, as in 2 and 6. Complex 7.2CH(2)Cl(2) crystallizes in monoclinic space group P2(1) with the following unit cell parameters at -170 degrees C: a = 18.169(3) Å, b = 19.678(4) Å, c = 25.036(4) Å, beta = 101.49(1) degrees, V = 8771.7 Å(3), Z = 4; the structure was refined on F to R (R(w)) = 7.36% (7.59%) using 10 782 unique reflections with F > 3sigma(F). Variable-temperature magnetic susceptibility studies have been carried out on powdered samples of complexes 2 and 5 in a 10.0 kG field in the 5.0-320.0 K range. The effective magnetic moment (&mgr;(eff)) for 2 gradually decreases from 8.61 &mgr;(B) per molecule at 320.0 K to 5.71 &mgr;(B) at 13.0 K and then increases slightly to 5.91 &mgr;(B) at 5.0 K. For 5, &mgr;(eff) gradually decreases from 10.54 &mgr;(B) per molecule at 320.0 K to 8.42 &mgr;(B) at 40.0 K, followed by a more rapid decrease to 6.02 &mgr;(B) at 5.0 K. On the basis of the crystal structure of 5 showing the single Mn(II) ion in each [Mn(4)O(2)](7+) subcore to be at a wingtip position, the Mn(II) ion in 2 was concluded to be at a wingtip position also. Employing the reasonable approximation that J(w)(b)(Mn(II)/Mn(III)) = J(w)(b)(Mn(III)/M(III)), where J(w)(b) is the magnetic exchange interaction between wingtip (w) and body (b) Mn ions of the indicated oxidation state, a theoretical chi(M) vs T expression was derived and used to fit the experimental molar magnetic susceptibility (chi(M)) vs T data. The obtained fitting parameters were J(w)(b) = -3.9 cm(-)(1), J(b)(b) = -9.2 cm(-)(1), and g = 1.80. These values suggest a S(T) = (5)/(2) ground state spin for 2, which was confirmed by magnetization vs field measurements in the 0.5-50.0 kG magnetic field range and 2.0-30.0 K temperature range. For complex 5, since the two bonds connecting the two [Mn(4)O(2)](7+) units are Jahn-Teller elongated and weak, it was assumed that complex 5 could be treated, to a first approximation, as consisting of weakly-interacting halves; the magnetic susceptibility data for 5 at temperatures >/=40 K were therefore fit to the same theoretical expression as used for 2, and the fitting parameters were J(w)(b) = -14.0 cm(-)(1) and J(b)(b) = -30.5 cm(-)(1), with g = 1.93 (held constant). These values suggest an S(T) = (5)/(2) ground state spin for each [Mn(4)O(2)](7+) unit of 5, as found for 2. The interactions between the subunits are difficult to incorporate into this model, and the true ground state spin value of the entire Mn(8) anion was therefore determined by magnetization vs field studies, which showed the ground state of 5 to be S(T) = 3. The results of the studies on 2 and 5 are considered with respect to spin frustration effects within the [Mn(4)O(2)](7+) units. Complexes 2 and 5 are EPR-active and -silent, respectively, consistent with their S(T) = (5)/(2) and S(T) = 3 ground states, respectively.

Journal Article↗
PubMed1996

Tetranuclear and Pentanuclear Vanadium(IV/V) Carboxylate Complexes: [V(4)O(8)(NO(3))(O(2)CR)(4)](2-) and [V(5)O(9)X(O(2)CR)(4)](2-) (X = Cl(-), Br(-)) Salts.

The syntheses and properties of tetra- and pentanuclear vanadium(IV,V) carboxylate complexes are reported. Reaction of (NBzEt(3))(2)[VOCl(4)] (1a) with NaO(2)CPh and atmospheric H(2)O/O(2) in MeCN leads to formation of (NBzEt(3))(2)[V(5)O(9)Cl(O(2)CPh)(4)] 4a; a similar reaction employing (NEt(4))(2)[VOCl(4)] (1b) gives (NEt(4))(2)[V(5)O(9)Cl(O(2)CPh)(4)] (4b). Complex 4a.MeCN crystallizes in space group P2(1)2(1)2(1) with the following unit cell dimensions at -148 degrees C: a = 13.863(13) Å, b = 34.009(43) Å, c = 12.773(11) Å, and Z = 4. The reaction between (NEt(4))(2)[VOBr(4)] (2a) and NaO(2)CPh under similar conditions gives (NEt(4))(2)[V(5)O(9)Br(O(2)CPh)(4)] (6a), and the use of (PPh(4))(2)[VOBr(4)] (2b) likewise gives (PPh(4))(2)[V(5)O(9)Br(O(2)CPh)(4)] (6b). Complex 6b crystallizes in space group P2(1)2(1)2(1) with the following unit cell dimensions at -139 degrees C: a = 18.638(3) Å, b = 23.557(4) Å, c = 12.731(2) Å, and Z = 4. The anions of 4a and 6b consist of a V(5) square pyramid with each vertical face bridged by a &mgr;(3)-O(2)(-) ion, the basal face bridged by a &mgr;(4)-X(-) (X = Cl, Br) ion, and a terminal, multiply-bonded O(2)(-) ion on each metal. The RCO(2)(-) groups bridge each basal edge to give C(4)(v)() virtual symmetry. The apical and basal metals are V(V) and V(IV), respectively (i.e., the anions are trapped-valence). The reaction of 1b with AgNO(3) and Na(tca) (tca = thiophene-2-carboxylate) in MeCN under anaerobic conditions gives (NEt(4))(2)[V(4)O(8)(NO(3))(tca)(4)] (7). Complex 7.H(2)O crystallizes in space group C2/c with the following unit cell dimensions at -170 degrees C: a = 23.606(4) Å, b = 15.211(3) Å, c = 23.999(5) Å, and Z = 4. The anion of 7 is similar to those of 4a and 6b except that the apical [VO] unit is absent, leaving a V(4) square unit, and the &mgr;(4)-X(-) ion is replaced with a &mgr;(4),eta(1)-NO(3)(-) ion. The four metal centers are now at the V(IV), 3V(V) oxidation level, but the structure indicates four equivalent V centers, suggesting an electronically delocalized system. Variable-temperature magnetic susceptibility data were collected on powdered samples of 4b, 6a, and 7 in the 2.00-300 K range in a 10 kG applied field. 4b and 6a both show a slow increase in effective magnetic moment (&mgr;(eff)) from approximately 3.6-3.7 &mgr;(B) at 320 K to approximately 4.5-4.6 &mgr;(B) at 11.0 K and then a slight decrease to approximately 4.2 &mgr;(B) at 2.00 K. The data were fit to the theoretical expression for a V(IV)(4) square with two exchange parameters J = J(cis)() and J' = J(trans)() (H = -2JS(i)()S(j)()): fitting of the data gave, in the format 4b/6a, J= +39.7/+46.4 cm(-)(1), J' = -11.1/-18.2 cm(-)(1) and g = 1.83/1.90, with the complexes possessing S(T) = 2 ground states. The latter were confirmed by magnetization vs field studies in the 2.00-30.0 K and 0.500-50.0 kG ranges: fitting of the data gave S(T) = 2 and D = 0.00 cm(-)(1) for both complexes, where D is the axial zero-field splitting parameter. Complex 7 shows a nearly temperature-independent &mgr;(eff) (1.6-2.0 &mgr;(B)) consistent with a single d electron per V(4) unit. The (1)H NMR spectra of 4b and 6a in CD(3)CN are consistent with retention of their pentanuclear structure on dissolution. The EPR spectrum of 7 in a toluene/MeCN (1:2) solution at approximately 25 degrees C yields an isotropic signal with a 29-line hyperfine pattern assignable to hyperfine interactions with four equivalent I = (7)/(2) (51)V nuclei.

Journal Article↗
PubMed1996

Solvate Molecule Effects and Unusual (57)Fe Mössbauer Line Broadening in the Valence Detrapping of Mixed-Valence [Fe(3)O(O(2)CCH(3))(6)(3-Et-py)(3)].S.

A new series of mixed-valence &mgr;(3)-oxo-bridged Fe(3)O complexes with the composition [Fe(3)O(O(2)CCH(3))(6)(3-Et-py)(3)].S, where 3-Et-py is 3-ethylpyridine and the solvate molecule S is either 0.5C(6)H(5)CH(3) (1), 0.5C(6)H(6) (2), CH(3)CN (3), or CH(3)CCl(3) (4), is reported. The complex [Fe(3)O(O(2)CCH(3))(6)(3-Et-py)(3)].0.5C(6)H(5)CH(3) (1) crystallizes in the orthorhombic space group Fdd2 which at 298 K has a unit cell with a = 22.726(8) Å, b = 35.643(14) Å, c = 20.816(6) Å, and Z = 16. Refinement with 5720 observed [F > 5sigma(F(o))] reflections gave R = 0.0337 and R(w) = 0.0390. An analysis of the bond lengths in complex 1 shows that it is the most valence-trapped Fe(3)O complex reported at room temperature. The complex [Fe(3)O(O(2)CCH(3))(6)(3-Et-py)(3)].CH(3)CCl(3) (4) crystallizes in the triclinic space group P&onemacr; which at 238 K has a unit cell with a = 12.764(2) Å, b = 13.1472(2) Å, c = 15.896(3) Å, alpha = 78.01(2) degrees, beta = 89.38(2) degrees, gamma = 61.38(1) degrees, and Z = 2. Refinement with 6264 observed [F > 5sigma(F(o))] reflections gave R = 0.0435 and R(w) = 0.0583. In this &mgr;(3)-oxo-bridged complex all three iron ions are inequivalent. Powder X-ray diffraction patterns taken at room temperature show that complexes 1 and 2 are isostructural and that complexes 3 and 4 are isostructural. Variable-temperature (57)Fe Mössbauer spectra were collected for all four complexes. The data for complexes 1 and 2 clearly indicate that these two complexes are totally valence trapped. On the other hand, Mössbauer spectra (43-293 K) for complexes 3 and 4 show that these two complexes become valence detrapped at temperatures near room temperature. Two doublets are seen at low temperature and they move together to become a single doublet at approximately 293 K. Examination of the line width versus temperature for each of the two components of the two doublets points to a curiosity. The two components of the "Fe(III)" doublet and the lower-velocity component of the "Fe(II)" doublet do not exhibit any line broadening, whereas the higher velocity "Fe(II)" component shows a surge in line width in the approximately 70-150 K range. Possible explanations for these unusual line width responses are discussed.

Journal Article↗
PubMed1996

Dinuclear Copper(II) Complexes Incorporating a New Septadentate Polyimidazole Ligand.

The dinuclear copper(II) complexes [Cu(2)(tmihpn)(prz)](ClO(4))(2).2CH(3)CN (6) and [Cu(2)(tmihpn)(O(2)CCH(3))](ClO(4))(2).CH(3)CN (7) were prepared, where tmihpn is the deprotonated form of N,N,N',N'-tetrakis[(1-methylimidazol-2-yl)methyl]-1,3-diaminopropan-2-ol and prz is the pyrazolate anion. The crystal structures of 6 and 7 were determined and revealed that both complexes contain bridging alkoxide ligands as well as bridging pyrazolate and acetate ions, respectively. Crystal data: compound 6, triclinic, P&onemacr;, a = 18.089(2) Å, b = 22.948(3) Å, c = 9.597(2) Å, alpha = 93.37(2) degrees, beta = 94.49(2) degrees, gamma = 81.69(2) degrees, V = 3925.1 Å(3), Z = 4; compound 7, triclinic, P&onemacr;, a = 12.417(2) Å, b = 15.012(3) Å, c = 10.699(2) Å, alpha = 104.76(2) degrees, beta = 102.63(2) degrees, gamma = 99.44(2) degrees, V = 1830.1 Å(3), Z = 2. In compound 6, the coordination geometry around both copper centers resembles a distorted square pyramid, while the stereochemistry around the copper centers in 7 is best described as trigonal bipyramidal. Both complexes display well-resolved isotropically shifted (1)H NMR spectra. Selective substitution studies and integration data have been used to definitively assign several signals to specific ligand protons. Results from the solution (1)H NMR studies suggest that the basal and apical imidazole groups do not exchange rapidly on the NMR time scale and the solid state structures of the complexes are retained in solution. In addition, the magnetochemical characteristics of 6 and 7 were determined and provide evidence for "magnetic orbital switching". Antiferromagnetic coupling in 6 (J = -130 cm(-)(1)) is strong, while the copper centers in compound 7 are ferromagnetically coupled (J = +16.4 cm(-1)). Differences in the magnetic behavior of the two copper centers have been rationalized using the "ligand orbital complementary" concept. The ground state magnetic orbitals involved in spin coupling in 6 (d(x)()()2(-)(y)()()2) are different from those in 7 (d(z)()()2).

Journal Article↗