Crystal structures of mixed-ligand oxocyano complexes of molybdenum(<scp>iv</scp>) and tungsten(<scp>iv</scp>) and their reactivity towards molecular oxygen studied by IR spectroscopy

Matoga, Dariusz; Szklarzewicz, Janusz; Samotus, Alina; Lewiński, K.

doi:10.1039/b202654f

Cited by 20 publications

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References 18 publications

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“…When the entering ligand is the CN ) ion, the reaction goes through [M(CN) 5 O] 3) (which can be isolated under proper conditions) [9,10,13] to [M(CN) 8 ] 4) [6b] and again, the intermediates in this reaction were not even detected spectroscopically, indicating fast processes and/or low stabilization of intermediates. On the other hand, in reactions with organic ligands (and not CN ) ) it is relatively easy to increase the coordination number to 7 [14].…”

Section: Introductionmentioning

confidence: 99%

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The Transition Products in Substitutional Photochemistry of [Mo(CN)8]4− – Theoretical Approach. X-ray Crystal Structure of (AsPh4)[W(bpy)(CN)6]

Stawski

Szklarzewicz

Lewiński

2006

Transition Met Chem

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Section: Introductionmentioning

confidence: 99%

“…On the other hand, in reactions with organic ligands (and not CN ) ) it is relatively easy to increase the coordination number to 7 [14]. Such a process occurs also when tetra-or penta-cyano complexes of Mo(IV) or W(IV) react with dioxygen [13]. This can suggest that the increase of coordination number from 6 to 7 is relatively easy.…”

Section: Introductionmentioning

confidence: 99%

The Transition Products in Substitutional Photochemistry of [Mo(CN)8]4− – Theoretical Approach. X-ray Crystal Structure of (AsPh4)[W(bpy)(CN)6]

Stawski

Szklarzewicz

Lewiński

2006

Transition Met Chem

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“…Such a mechanism is typical for the d 2 metal complexes [23]. The following reaction scheme is postulated.…”

Section: Kinetic Measurementsmentioning

confidence: 97%

A new route to the asymmetric Schiff base ligands. The ligand exchange in [Mo(CN)3O(salhy)]2? ion. Kinetics and mechanism

Szklarzewicz

Gruszewska

2005

Transition Met Chem

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The kinetics of the ligand exchange in (PPh 4 ) 2 [Mo(CN) 3 O(salhy)] AE 6H 2 O (Hsalhy = salicylaldehyde hydrazone) by a solvent molecule and by 2,2¢-bipyridine (bpy) have been studied in EtOH. For the ligand exchange by a solvent molecule the pseudo-first order rate constant equals k obs = 3.2 (±0.2) · 10 )3 s ), while for the exchange by a bpy molecule k obs ¼ 3.5 (±0.2) · 10 )3 s )1 (t ¼ 25°C), DH à ¼ 56 (±7) KJ mol )1 , DS à = )104 (±8) J mol )1 K )1 . It was found, that all reactions proceed via the same mechanism which involves the chelate ring opening cis to the Mo@O bond. The mechanism of the reaction was proposed and was proved by the synthesis of (PPh 4 ) 2 [Mo(CN) 3 O(N-pic)] AE 2.5H 2 O (N-pic denotes that the nitrogen of picolinic acid is trans to Mo@O) by ligand exchange in EtOH, while in aqueous solution the O-pic analogue is formed exclusively.

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“…The anion exhibits a dinuclear structure comprising two identical {MoOCl 3 (Pyz)} halves linked by a single bridging oxido ligand. With the latter resting upon the inversion centre of the P2 1 /n space group, [23] [Mo 2 O 6 (Pyz)] 2.449(8) oxide [24] […”

Section: Structural Studiesmentioning

confidence: 99%

Pyrazine‐Assisted Dimerization of Molybdenum(V): Synthesis and Structural Characterization of Novel Dinuclear and Tetranuclear Complexes

2010

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12 pagesInternational audienceReactions of pyrazine (Pyz = C4H4N2) with [MoOCl4(H2O)]– or [MoOBr4]– afforded a series of complexes, dinuclear [(MoOX4)2(Pyz)]2– (X = Cl, Br), [{MoOCl3(Pyz)}2O]2– and tetranuclear [(Mo2O4Cl4)2(Pyz)2]4– anions, with N-donor ligands engaged either in monodentate or bidentate bridging coordination. A dinuclear [(MoOX4)2(Pyz)]2– ion, which may be viewed as a linkage of two mononuclear subunits with a bidentate pyrazine, crystallizes either as a PyH+ (pyridinium cation, C5H5NH+; compound 1), a {(C2H5)4N}+ (compound 2) or a {(C6H5)4P}+ salt (compounds 3 and 4). In (PyH)2- [{MoOCl3(Pyz)}2O] (5) with an anti-{Mo2O3}4+ core, pyrazine is bound to the metal through only one nitrogen atom. The tetranuclear [(Mo2O4Cl4)2(Pyz)2]4– ion, a linkage of two metal–metal bonded {Mo2O4}2+ cores with a pair of bidentate pyrazines, is found in two compounds, (MeNC5H5)2(PyzH2)- [(Mo2O4Cl4)2(Pyz)2] (6) [MeNC5H5 + = N-methylpyridinium cation, PyzH2 2+ = pyrazinium(2+) cation] and (PyH)4- [(Mo2O4Cl4)2(Pyz)2]·2CH3CN (7). In the presence of methanol, dinuclear {(C6H5)4P}2[(MoOBr4)2(Pyz)]·2CH3CN (4) was transformed directly into tetranuclear (PyH)4[(Mo2O4Br4)2- (Pyz)2]·2CH3CN (8). All compounds were fully characterized by X-ray crystallography and IR spectroscopy. The compounds containing the [(MoOX4)2(Pyz)]2– ions display an irreversible electrochemical reduction behaviour. Temperature- dependent magnetic measurements on {(C6H5)4P}2- [(MoOX4)2(Pyz)]·2CH3CN (X = Cl for 3, X = Br for 4) reveal a weak ferromagnetic coupling across the pyrazine bridge between a pair ofMoV S = 1/2 spins. The magnetic properties of {(C2H5)4N}2[(MoOCl4)2(Pyz)] (2), another compound with dinuclear complex anions, are dominated by antiferromagnetic intermolecular interactions

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Crystal structures of mixed-ligand oxocyano complexes of molybdenum(iv) and tungsten(iv) and their reactivity towards molecular oxygen studied by IR spectroscopy

Cited by 20 publications

References 18 publications

The Transition Products in Substitutional Photochemistry of [Mo(CN)8]4− – Theoretical Approach. X-ray Crystal Structure of (AsPh4)[W(bpy)(CN)6]

The Transition Products in Substitutional Photochemistry of [Mo(CN)8]4− – Theoretical Approach. X-ray Crystal Structure of (AsPh4)[W(bpy)(CN)6]

A new route to the asymmetric Schiff base ligands. The ligand exchange in [Mo(CN)3O(salhy)]2? ion. Kinetics and mechanism

Pyrazine‐Assisted Dimerization of Molybdenum(V): Synthesis and Structural Characterization of Novel Dinuclear and Tetranuclear Complexes

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