Syntheses, structures, and magnetic properties of a family of tetra-, hexa-, and nonanuclear Mn/Ni heterometallic clusters.

A family of Mn(III)/Ni(II) heterometallic clusters, [Mn(III)(4)Ni(II)(5)(OH)(4)(hmcH)(4)(pao)(8)Cl(2)]·5DMF (1·5DMF), [Mn(III)(3)Ni(II)(6)(N(3))(2)(pao)(10)(hmcH)(2)(OH)(4)]Br·2MeOH·9H(2)O (2·2MeOH·9H(2)O), [Mn(III)Ni(II)(5)(N(3))(4)(pao)(6)(paoH)(2)(OH)(2)](ClO(4))·MeOH·3H(2)O (3·MeOH·3H(2)O), and [Mn(III)(2)Ni(II)(2)(hmcH)(2)(pao)(4)(OMe)(2)(MeOH)(2)]·2H(2)O·6MeOH (4·2H(2)O·6MeOH) [paoH = pyridine-2-aldoxime, hmcH(3) = 2, 6-Bis(hydroxymethyl)-p-cresol], has been prepared by reactions of Mn(II) salts with [Ni(paoH)(2)Cl(2)], hmcH(3), and NEt(3) in the presence or absence of NaN(3) and characterized. Complex 1 has a Mn(III)(4)Ni(II)(5) topology which can be described as two corner-sharing [Mn(2)Ni(2)O(2)] butterfly units bridged to an outer Mn atom and a Ni atom through alkoxide groups. Complex 2 has a Mn(III)(3)Ni(II)(6) topology that is similar to that of 1 but with two corner-sharing [Mn(2)Ni(2)O(2)] units of 1 replaced with [Mn(3)NiO(2)] and [MnNi(3)O(2)] units as well as the outer Mn atom of 1 substituted by a Ni atom. 1 and 2 represent the largest 3d heterometal/oxime clusters and the biggest Mn(III)Ni(II) clusters discovered to date. Complex 3 possesses a [MnNi(5)(µ-N(3))(2)(µ-OH)(2)](9+) core, whose topology is observed for the first time in a discrete molecule. Careful examination of the structures of 1-3 indicates that the Mn/Ni ratios of the complexes are likely associated with the presence of the different coligands hmcH(2-) and/or N(3)(-). Complex 4 has a Mn(III)(2)Ni(II)(2) defective double-cubane topology. Variable-temperature, solid-state dc and ac magnetization studies were carried out on complexes 1-4. Fitting of the obtained M/(Nµ(B)) vs H/T data gave S = 5, g = 1.94, and D = -0.38 cm(-1) for 1 and S = 3, g = 2.05, and D = -0.86 cm(-1) for 3. The ground state for 2 was determined from ac data, which indicated an S = 5 ground state. For 4, the pairwise exchange interactions were determined by fitting the susceptibility data vs T based on a 3-J model. Complex 1 exhibits out-of-phase ac susceptibility signals, indicating it may be a SMM.

The use of phosphonates for constructing 3d-4f clusters at high oxidation states: synthesis and characterization of two unusual heterometallic CeMn complexes.

The use of phosphonic acids in the synthesis of mixed-metal CeMn complexes has led to the formation of two phosphonate complexes with unusual topologies: [Ce(2)Mn(6)O(6)(OH)(5)(t-BuPO(3))(6)(O(2)CMe)(3)] x 53 H(2)O (1 x 53 H(2)O) and [Ce(22)Mn(12)O(34)(MePO(3))(12)(O(2)CMe)(33)(OMe)(6)(NO(3))(H(2)O)(12)](n) (2). The two mixed-metal CeMn complexes were both prepared from a reaction system containing Mn(O(2)CMe)(2) and (NH(4))(2)[Ce(NO(3))(6)] with similar procedures except for using different phosphonic acids (tert-butylphosphonic acid and methylphosphonic acid, respectively) as coligands. Both complexes possess rare topology of triangular type, with compound 1 being a 0D discrete cluster, whereas, compound 2 is a 1D polymer. The octanuclear core of complex 1 is composed of three symmetry equivalent distorted cubanes {Ce(IV)(2)Mn(IV)(2)O(2)(OH)(2)} sharing a trigonal-bipyramidal unit {Ce(IV)(2)(OH)(3)} in the centre. Compound 2 is a one-dimensional chain polymer of identical Ce(22)Mn(12)O(34) units linked together by NO(3)(-) and MeCO(2)(-) groups, while the Ce(22)Mn(12)O(34) unit is constituted by two centrosymmetric Ce(9)(IV)Ce(2)(III)Mn(IV)(6)O(17) subunits, which features three identical distorted cubanes {Ce(IV)(2)Mn(IV)(2)O(4)} connecting to a central trigonal-bipyramidal unit {Ce(IV)(3)O(2)}, and two additional Ce(III) ions capping the top and bottom of the central trigonal bipyramid by six MePO(3)(2-) ligands. Complexes 1 and 2 are the first high-nuclearity Mn/Ln aggregates reported to date using phosphonates as ligands. Magnetic susceptibility measurements reveal that compound 1 displays dominant ferromagnetic interactions between the adjacent metal ions with the best fit parameters for the exchanges are J(1) = 6.186 cm(-1), J(2) = 4.172 cm(-1), and with a result of S = 9 ground state confirmed by the M versus HT(-1) data, which indicates the spins of all the six Mn(IV) ions in the cluster are parallel to each other. In contrast, the data for 2 reveals overall antiferromagnetic couplings within the cluster and a resulting S = 6 ground state. Both the in-phase signal chi'(M)T and out-of-phase signal chi''(M) of the two complexes exhibit frequency-dependent below approximate 3 K.

Synthesis and characterization of a family of penta- and tetra-manganese(III) complexes derived from an assembly system containing tert-butylphosphonic acid.

A family of manganese complexes, [Mn 5O 3( t-BuPO 3) 2(MeCOO) 5(H 2O)(phen) 2] ( 1), [Mn 5O 3( t-BuPO 3) 2(PhCOO) 5(phen) 2] ( 2), [Mn 4O 2( t-BuPO 3) 2(RCOO) 4(bpy) 2] (R = Me, ( 3); R = Ph, ( 4)), NBu (n) 4[Mn 4O 2(EtCOO) 3(MeCOO) 4(pic) 2] ( 5), NR' 4[Mn 4O 2( i-PrCOO) 7(pic) 2] (R' = Bu (n) , ( 6); R' = Et, ( 7)), were synthesized and characterized. The seven manganese clusters were all prepared from a reaction system containing tert-butylphosphonic acid, Mn(O 2CR) 2 (R = Me, Ph) and NR' 4MnO 4 (R' = Bu (n) , Et) with similar procedures except for using different N-containing ligands (1,10-phenanthroline (phen), 2,2'-bipyridine (bpy) and picolinic acid (picH)) as coligands. The structures of these complexes vary with the N-containing donors. Both the cores of complexes 1 and 2 feature three mu 3-O and two capping t-BuPO 3 (2-) groups bridging five Mn (III) atoms to form a basket-like cage structure. Complexes 3 and 4 both have one [Mn 4(mu 3-O) 2] (8+) core with four coplanar Mn (III) atoms disposed in an extended "butterfly-like" arrangement and two capping mu 3- t-BuPO 3 (2-) binding to three manganese centers above and below the Mn 4 plane. Complexes 5, 6, and 7 all possess one [Mn 4(mu 3-O) 2] (8+) core just as complexes 3 and 4, but they display a folded "butterfly-like" conformation with the four Mn (III) atoms nonplanar. Thus, the seven compounds are classified into three types, and three representative compounds 1.2H 2O.MeOH.MeCN , 3.6H 2O.2MeCOOH , and 5.0.5H 2O have been characterized by IR spectroscopy, ESI-MS spectroscopy, magnetic measurements and in situ UV-vis-NIR spectroelectrochemical analysis. Magnetic susceptibility measurements reveal the existence of both ferromagnetic and antiferromagnetic interactions between the adjacent Mn (III) ions in compound 1.2H 2O.MeOH.MeCN , and antiferromagnetic interactions in 3.6H 2O.2MeCOOH and 5.0.5H 2O. Fitting the experimental data led to the following parameters: J 1 = -2.18 cm (-1), J 2 = 6.93 cm (-1), J 3 = -13.94 cm (-1), J 4 = -9.62 cm (-1), J 5 = -11.17 cm (-1), g = 2.00 ( 1.2H 2O.MeOH.MeCN ), J 1 = -5.41 cm (-1), J 2 = -35.44 cm (-1), g = 2.13, zJ' = -1.55 cm (-1) ( 3.6H 2O.2MeCOOH ) and J 1 = -2.29 cm (-1), J 2 = -35.21 cm (-1), g = 2.02, zJ' = -0.86 cm (-1) ( 5.0.5H 2O ).

[2-(2-Pyridyl)-1H-benzimidazole-kappa2N2,N3]bis(p-toluato-kappa2O,O')manganese(II).

In the title compound, [Mn(C8H7O2)2(C12H9N3)], the manganese(II) centre is surrounded by three bidentate chelating ligands, namely, one 2-(2-pyridyl)benzimidazole ligand [Mn-N = 2.1954 (13) and 2.2595 (14) A] and two p-toluate ligands [Mn-O = 2.1559 (13)-2.2748 (14) A]. It displays a severely distorted octahedral geometry, with cis angles ranging from 58.87 (4) to 106.49 (5) degrees. Intermolecular C-H...O hydrogen bonds between the p-toluate ligands link the molecules into infinite chains, and every two neighbouring chains are further coupled by N-H...O and C-H...O hydrogen bonds between the 2-(2-pyridyl)benzimidazole and p-toluate ligands, leading to an infinite ribbon-like double-chain packing mode. The complete solid-state structure can be described as a three-dimensional supramolecular framework, stabilized by these intermolecular hydrogen-bonding interactions and possible C-H...pi interactions, as well as stacking interactions involving the 2-(2-pyridyl)benzimidazole ligands.

Bis(mu4-butane-1,4-dithiolato)bis[hexacarbonyldiiron(II)(Fe-Fe)].

The novel title double-butterfly Fe/S cluster complex, [Fe(4)(C(4)H(8)S(2))(2)(CO)(12)], which is structurally similar to the active site of the Fe-only hydrogenases, contains two inversion-related Fe(2)S(2)(CO)(6) subcluster cores connected by two equivalent butyl chains to afford a 16-membered macrocycle. The formation of the 16-membered macrocycle has an influence on the C-S-Fe angles, while the Fe-Fe and Fe-S bond lengths remain similar to those in related complexes.

Aqua(dipicolinato-kappa(3)O,N,O')(1H-imidazole-kappaN(3))(1,10-phenanthroline-N,N')manganese(II).

In the title compound, [Mn(C(7)H(3)NO(4))(C(3)H(4)N(2))(C(12)H(8)N(2))(H(2)O)], the Mn(II) centre is surrounded by one bidentate phenanthroline ligand [Mn-N = 2.383 (3) and 2.421 (3) A], one tridentate dipicolinate ligand [Mn-N = 2.300 (3) A, and Mn-O = 2.300 (2) and 2.357 (2) A], one monodentate imidazole ligand [Mn-N = 2.238 (3) A] and one water molecule [Mn-O = 2.157 (3) A]. It displays a distorted pentagonal-bipyramidal geometry, with neighbouring angles within the equatorial plane ranging from 68.05 (9) to 77.48 (10) degrees . Intermolecular O-H...O hydrogen bonds link the molecules into infinite chains. The chains are crosslinked by hydrogen bonds involving the carboxyl O atoms of the dipicolinate ligand and the protonated imidazole N atom, leading to an infinite two-dimensional network sheet packing mode. The complete solid-state structure can be described as a three-dimensional supramolecular framework, stabilized by these intermolecular hydrogen-bonding interactions and pi-pi stacking interactions involving the phenanthroline rings.

Diiron models for the active site of Fe-only hydrogenase with terminal organosulfur ligation: synthesis, structures and electrochemistry.

Diiron model complexes (micro-SCH(2)CH(2)CH(2)S)Fe(2)(CO)(5)L with thioether-substitution, L=S(CH(2)CH(3))(2) (2), S(CH(2)CH(3))(CH(2)CH(2)Cl) (3), S(CH(2)CH(3))(C(6)H(5)) (4), or sulfoxide-substitution, L=SO(CH(2)CH(2)CH(3))(2) (5), SO(CH(3))(2) (6), were synthesized as active site analogues of Fe-only hydrogenase. The organosulfur ligands were introduced into the diiron centers via moderately stable intermediates following two routes. The X-ray crystallographic structures of complexes 2-6 show the apical positions of terminal organosulfur ligands. The electrochemical behaviors of the model complexes were investigated, especially for the interesting properties of the derivative of 6 which is proposed to be the first model with weak donor ligand similar to CO.

Poly[[[aquamanganese(II)]-mu2-4,4'-bipyridine-mu3-succinato] 4,4'-bipyridine hemisolvate].

The polymeric title complex, [[Mn(C(4)H(4)O(4))(C(10)H(8)N(2))(H(2)O)].0.5C(10)H(8)N(2)](n), possesses a three-dimensional open-framework structure, with the solvate 4,4'-bipyridine (bipy) molecules, which lie around centers of inversion, clathrated in the channels of the framework. The Mn(II) center is surrounded by three succinate (succ) ligands, one water molecule and two bipy ligands, and displays a slightly distorted octahedral coordination environment, with cis angles ranging from 84.14 (12) to 96.56 (11) degrees. Each succ dianion coordinates to three Mn(II) atoms, thus acting as a bridging tridentate ligand; in turn, the Mn(II) atoms are bridged by three succ ligands, thus forming a two-dimensional Mn-succ sheet pillared by the bridging bipy ligands. Two hydrogen-bonding interactions, involving the water molecules and the carboxy O atoms of the succ ligands, are present in the crystal structure.

catena-Poly[[aqua(2,2'-bipyridine-kappa2N,N')manganese(II)]-mu-terephthalato-kappa3O,O':O"].

The title complex, [Mn(C(8)H(4)O(4))(C(10)H(8)N(2))(H(2)O)](n), takes the form of a zigzag chain, with the terephthalate dianion (tp) acting as a tridentate ligand. The Mn(II) center is surrounded by two tp ligands, one water molecule and one 2,2'-bipyridine (bipy) ligand and exhibits a severely distorted octahedral coordination environment, with cis angles ranging from 57.31 (8) to 123.97 (11) degrees. The complete solid-state structure can be described as a three-dimensional supramolecular framework stabilized by hydrogen-bonding interactions involving the coordinated water molecule and the carboxy O atoms of the tp ligands, and by pi-pi stacking interactions involving the bipy rings and the benzene ring of the tp ligand.