Intra‐ and Intermolecular H···Cl–Ni Bonding Patterns in a Series of Highly Preorganized Dinuclear Nickel(II) Complexes

Nie, Feng‐Mei; Leibeling, Guido; Demeshko, Serhiy; Dechert, Sebastian; Meyer, Franc

doi:10.1002/ejic.200600889

Cited by 16 publications

(5 citation statements)

References 27 publications

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“…There are eight structurally characterized dinuclear octahedral nickel(II) complexes of bis-tetradentate pyrazolate -based ligands in the literature. − As expected, the Ni–N pyrazolate bonds are slightly shorter, due to the negatively charged nature of the pyrazolate ring, 1.943(4)–2.144(3) Å, than the Ni–N triazole bonds in the triazole complexes reported in this work, 2.040(3)–2.119(4) Å (Table ). The Ni–N amine and Ni–N py bonds in the pyrazolate complexes (2.096(3)–2.205(1) and 2.043(3)–2.178(5) Å, respectively) are similar or slightly longer than in our triazole complexes (2.093(3)–2.132(4) and 2.039(4)–2.082(3) Å, respectively, Table ).…”

Section: Resultssupporting

confidence: 72%

Di- and Tetra-Nuclear Copper(II), Nickel(II), and Cobalt(II) Complexes of Four Bis-Tetradentate Triazole-Based Ligands: Synthesis, Structure, and Magnetic Properties

et al. 2012

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Four bis-tetradentate N(4)-substituted-3,5-{bis[bis-N-(2-pyridinemethyl)]aminomethyl}-4H-1,2,4-triazole ligands, L(Tz1)-L(Tz4), differing only in the triazole N(4) substituent R (where R is amino, pyrrolyl, phenyl, or 4-tertbutylphenyl, respectively) have been synthesized, characterized, and reacted with M(II)(BF(4))(2)·6H(2)O (M(II) = Cu, Ni or Co) and Co(SCN)(2). Experiments using all 16 possible combinations of metal salt and L(TzR) were carried out: 14 pure complexes were obtained, 11 of which are dinuclear, while the other three are tetranuclear. The dinuclear complexes include two copper(II) complexes, [Cu(II)(2)(L(Tz2))(H(2)O)(4)](BF(4))(4) (2), [Cu(II)(2)(L(Tz4))(BF(4))(2)](BF(4))(2) (4); two nickel(II) complexes, [Ni(II)(2)(L(Tz1))(H(2)O)(3)(CH(3)CN)](BF(4))(4)·0.5(CH(3)CN) (5) and [Ni(II)(2)(L(Tz4))(H(2)O)(4)](BF(4))(4)·H(2)O (8); and seven cobalt(II) complexes, [Co(II)(2)(L(Tz1))(μ-BF(4))](BF(4))(3)·H(2)O (9), [Co(II)(2)(L(Tz2))(μ-BF(4))](BF(4))(3)·2H(2)O (10), [Co(II)(2)(L(Tz3))(H(2)O)(2)](BF(4))(4) (11), [Co(II)(2)(L(Tz4))(μ-BF(4))](BF(4))(3)·3H(2)O (12), [Co(II)(2)(L(Tz1))(SCN)(4)]·3H(2)O (13), [Co(II)(2)(L(Tz2))(SCN)(4)]·2H(2)O (14), and [Co(II)(2)(L(Tz3))(SCN)(4)]·H(2)O (15). The tetranuclear complexes are [Cu(II)(4)(L(Tz1))(2)(H(2)O)(2)(BF(4))(2)](BF(4))(6) (1), [Cu(II)(4)(L(Tz3))(2)(H(2)O)(2)(μ-F)(2)](BF(4))(6)·0.5H(2)O (3), and [Ni(II)(4)(L(Tz3))(2)(H(2)O)(4)(μ-F(2))](BF(4))(6)·6.5H(2)O (7). Single crystal X-ray structure determinations revealed different solvent content from that found by microanalysis of the bulk sample after drying under a vacuum and confirmed that 5', 8', 9', 11', 12', and 15' are dinuclear while 1' and 7' are tetranuclear. As expected, magnetic measurements showed that weak antiferromagnetic intracomplex interactions are present in 1, 2, 4, 7, and 8, stabilizing a singlet spin ground state. All seven of the dinuclear cobalt(II) complexes, 9-15, have similar magnetic behavior and remain in the [HS-HS] state between 300 and 1.8 K.

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Section: Resultssupporting

confidence: 72%

Di- and Tetra-Nuclear Copper(II), Nickel(II), and Cobalt(II) Complexes of Four Bis-Tetradentate Triazole-Based Ligands: Synthesis, Structure, and Magnetic Properties

et al. 2012

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“…The chlorido-aqua coordination motif can thus be considered as a dynamic bridging unit. This process likely goes via dissociation of the water molecule and possibly via a chlorido bridged intermediate, followed by reinsertion of water. Exchange of H 2 O in related (H)O···H–O(H) bridging units was previously shown to proceed rapidly …”

Section: Resultsmentioning

confidence: 99%

Establishing the Family of Diruthenium Water Oxidation Catalysts Based on the Bis(bipyridyl)pyrazolate Ligand System

et al. 2016

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A bis(bipyridyl)pyrazolate ((Me)bbp(-)) has recently been introduced as a rugged dinucleating, bis(tridentate) ligand for the formation of efficient diruthenium water oxidation catalysts (J. Am. Chem. Soc. 2014, 136, 24-27). Now, detailed protocols for the synthesis of a whole family of such dinuclear ruthenium complexes [{Ru(pyR(2))2}2(μ-(R1)bbp)(X,Y)](2+) based on the bis(bipyridyl)pyrazolate scaffold are reported. The isolation of a synthetic key intermediate allowed the straightforward introduction of different pyridines as axial ligands. Thereby, a set of complexes with different substituents at the pyrazolate backbone (R(1) = Br, H, Me), different pyridines as axial ligand (R(2) = H, NMe2, SO3), and different (non)bridging units in the in,in-position (X,Y = Cl, H2O, OAc) has been prepared and thoroughly characterized. Complexes of the type [{Ru(pyR(2))2}2(μ-(R1)bbp)(μ-OAc)](2+), with an exogenous acetato bridge, have been used as catalyst precursors in catalytic water oxidation experiments with a sacrificial oxidant. The effect of substitution on the pyrazole core of the (R1)bbp(-) ligand as well as on the pyridine ligands on both electrochemistry and catalytic activity has been systematically investigated. The catalyst stability, reflected by the turnover number, is crucially determined by the substituent at the pyrazolate ligand (R(1) = Me > H > Br). In contrast, the axial pyridine ligands modulate the rate of the catalytic process, expressed by the initial turnover frequency (R(2) = H > NMe2H(+)).

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“…Meyer and co-workers have shown that ligand (L 1 )is capable of producing dinuclear systems in which the metal ions [copper(II), 10 zinc(II), 11 nickel(II) 12 ] are singly-bridged by the central pyrazolate moiety and coordinated to the tertiary amine and the two pyridine donors of the pendant arms, with the two last positions occupied by solvent or anion molecules. This is exactly the binding mode we wish to see adopted, but for iron(II), and preferably with the last two positions occupied by coordinating anions that are known to help confer SCO-activity on the iron centres, such as NCS and NCSe.…”

Section: Introductionmentioning

confidence: 99%

Two dinuclear iron(ii) complexes K[Fe2(L1)(SCN)4]·2(C3H8O) and [Fe2(L1)(SeCN)3(C5H5N)]·H2O are stabilised in the ‘[HS–LS]’ state by a bis-tetradentate pyrazolate-based ligand

2011

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Two air-sensitive dinuclear iron(II) complexes, K[Fe(II)(2)(L(1))(SCN)(4)]·2(C(3)H(8)O) (1) and [Fe(II)(2)(L(1))(SeCN)(3)(C(5)H(5)N)]·H(2)O (2), of 3,5-bis[N,N-bis(2-pyridylmethyl)aminomethyl]-1H-pyrazolate [(L(1))(-)] have been prepared. Interestingly, complex 1 is anionic, featuring four coordinated SCN(-) anions and a potassium counterion whereas complex 2 is neutral, containing a coordinated pyridine molecule and only three coordinated SeCN(-) anions. These are the first iron complexes reported for this type of ligand. Magnetic measurements and Mössbauer spectra show that both 1 and 2 are in a '[HS-LS]' mixed spin state between 300 and 2 K.

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Intra‐ and Intermolecular H···Cl–Ni Bonding Patterns in a Series of Highly Preorganized Dinuclear Nickel(II) Complexes

Cited by 16 publications

References 27 publications

Di- and Tetra-Nuclear Copper(II), Nickel(II), and Cobalt(II) Complexes of Four Bis-Tetradentate Triazole-Based Ligands: Synthesis, Structure, and Magnetic Properties

Di- and Tetra-Nuclear Copper(II), Nickel(II), and Cobalt(II) Complexes of Four Bis-Tetradentate Triazole-Based Ligands: Synthesis, Structure, and Magnetic Properties

Establishing the Family of Diruthenium Water Oxidation Catalysts Based on the Bis(bipyridyl)pyrazolate Ligand System

Two dinuclear iron(ii) complexes K[Fe2(L1)(SCN)4]·2(C3H8O) and [Fe2(L1)(SeCN)3(C5H5N)]·H2O are stabilised in the ‘[HS–LS]’ state by a bis-tetradentate pyrazolate-based ligand

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