Dioxotetracyano-complexes of molybdenum (IV) and tungsten (IV) and their vibrational spectra

Samotus, Alina; Dudek, Magdalena; Kanas, Aleksandra

doi:10.1016/0022-1902(75)80676-2

Cited by 36 publications

(5 citation statements)

References 9 publications

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“…Contrary to these four metals, only very few molybdenum(IV) and tungsten(IV) dioxo complexes have been described. These are the trans -[M(O) 2 (CN) 4 ] 4- ions and the matrix-isolated trans -[M(O) 2 (CO) 4 ] (M = Mo, W) complexes …”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of a Stable trans-Dioxo Tungsten(IV) Complex and Series of Mono-Oxo Molybdenum(IV) and Tungsten(IV) Complexes. Structural and Electronic Effects of π-Bonding in trans-[M(O)(X)(dppe)₂]^+/0 Systems

Bendix

Bøgevig

1998

Inorg. Chem.

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trans-[W(O)(F)(dppe)(2)](BF(4)) (dppe = Ph(2)PCH(2)CH(2)PPh(2), 1,2-bis(diphenylphosphino)ethane) (10) has been synthesized. From this, the neutral trans-[W(O)(2)(dppe)(2)].2CH(3)OH (11) was prepared by a hydrolysis and deprotonation reaction with Et(4)NOH in methanol/water. Together with the analogous molybdenum compound (2) this compound afforded by substitution under acid conditions salts of trans-[M(O)(X)(dppe)(2)](+) ions (M = Mo, W; X = OH, OCH(3), Cl, Br, I, NCS) and trans-[Mo(O)(N(3))(dppe)(2)](CF(3)SO(3)) (9). All the compounds have low-spin d(2) electronic configuration. The compounds were characterized by (31)P{(1)H} NMR, positive FAB-ionization mass spectrometry, UV-vis spectroscopy, and vibrational spectroscopy. X-ray crystallographic studies were carried out on compounds 10, 11, trans-[W(O)(OH)(dppe)(2)](ClO(4)) (12), and trans-[W(O)(NCS)(dppe)(2)](BPh(4)) (16). The electronic spectra of the mono-oxo species are consistent with the lowest energy transitions being of d(xy)() --> {d(zx)(), d(yz)()} character. No ligand-field transitions are observed for the dioxo tungsten complex. Identical pi-spectrochemical series were found for the two metals. The shielding of the phosphorus nuclei determined by (31)P{(1)H} NMR is significantly influenced by the nature of the axial ligands.

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Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of a Stable trans-Dioxo Tungsten(IV) Complex and Series of Mono-Oxo Molybdenum(IV) and Tungsten(IV) Complexes. Structural and Electronic Effects of π-Bonding in trans-[M(O)(X)(dppe)₂]^+/0 Systems

Bendix

Bøgevig

1998

Inorg. Chem.

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“…K 4 [Mo(CN) 8 ]·2H 2 O, (PPh 4 ) 2 [Mo(CN) 4 O(NH 3 )]·2H 2 O, Cs 2 Na[Mo(CN) 5 O], K 3 Na[Mo(CN) 4 O 2 ]·6H 2 O, and K 5 [Mo(CN) 7 ]·H 2 O were prepared according to literature procedures, their identities and purity confirmed by elemental analyses and IR spectroscopy. All other chemicals including hydrazine monohydrate (98%, Aldrich) were of analytical grade and were used as supplied.…”

Section: Methodsmentioning

confidence: 99%

Ligand-Field Photolysis of [Mo(CN)₈]⁴⁻ in Aqueous Hydrazine: Trapped Mo(II) Intermediate and Catalytic Disproportionation of Hydrazine by Cyano-Ligated Mo(III,IV) Complexes

et al. 2008

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The substitutional photolysis of K4[Mo(CN)8].2H2O in 98% N2H4.H2O has been investigated in detail. A molybdenum(II) intermediate, K5[Mo(CN)7].N2H4, is isolated in the primary stage of the reaction that involves the oxidation of N2H4 to N2, as evidenced by the analysis of evolving gases. The powder X-ray crystal structure of K5[Mo(CN)7].N2H4 indicates the pentagonal bipiramidal geometry of the anion and the presence of N2H4 in proximity to the CN(-) ligands. The salt is characterized by means of EDS, IR, UV-vis, and EPR spectroscopy as well as cyclic voltammetry measurements. The secondary stages of photolysis, involving the catalytic decomposition of N2H4 into NH3 and N2, lead to the formation of a molybdenum(IV) complex, [Mo(CN)4O(NH3)]2-. The monitoring of the amounts of evolving gases combined with UV-vis and EPR spectroscopic measurements at various stages of photolysis indicate that the molybdenum(III,IV) couple is catalytically active. The scheme of the catalytic decomposition of hydrazine is presented and discussed.

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“…The complexes K 12 and Schiff bases N,NЈ-bis(salicylidene)ethylenediamine and N,NЈbis(salicylidene)propane-1,3-diamine 13 were prepared by published methods. Other reagents and solvents of analytical purity were used as supplied.…”

Section: Methodsmentioning

confidence: 99%

Oxocyano complexes of molybdenum(IV) and tungsten(IV) with Schiff base ligands derived from salicylaldehyde and aliphatic amines. Crystal structure of [PPh4]2[Mo(CN)3O(ensal)]·5.5H2O (Hensal = N-salicylideneethylenediamine)

Nowicka¹,

Samotus²,

Szklarzewicz³

et al. 1998

J. Chem. Soc., Dalton Trans.

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Dioxotetracyano-complexes of molybdenum (IV) and tungsten (IV) and their vibrational spectra

Cited by 36 publications

References 9 publications

Synthesis and Characterization of a Stable trans-Dioxo Tungsten(IV) Complex and Series of Mono-Oxo Molybdenum(IV) and Tungsten(IV) Complexes. Structural and Electronic Effects of π-Bonding in trans-[M(O)(X)(dppe)₂]^+/0 Systems

Synthesis and Characterization of a Stable trans-Dioxo Tungsten(IV) Complex and Series of Mono-Oxo Molybdenum(IV) and Tungsten(IV) Complexes. Structural and Electronic Effects of π-Bonding in trans-[M(O)(X)(dppe)₂]^+/0 Systems

Ligand-Field Photolysis of [Mo(CN)₈]⁴⁻ in Aqueous Hydrazine: Trapped Mo(II) Intermediate and Catalytic Disproportionation of Hydrazine by Cyano-Ligated Mo(III,IV) Complexes

Oxocyano complexes of molybdenum(IV) and tungsten(IV) with Schiff base ligands derived from salicylaldehyde and aliphatic amines. Crystal structure of [PPh4]2[Mo(CN)3O(ensal)]·5.5H2O (Hensal = N-salicylideneethylenediamine)

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Dioxotetracyano-complexes of molybdenum (IV) and tungsten (IV) and their vibrational spectra

Cited by 36 publications

References 9 publications

Synthesis and Characterization of a Stable trans-Dioxo Tungsten(IV) Complex and Series of Mono-Oxo Molybdenum(IV) and Tungsten(IV) Complexes. Structural and Electronic Effects of π-Bonding in trans-[M(O)(X)(dppe)2]+/0 Systems

Synthesis and Characterization of a Stable trans-Dioxo Tungsten(IV) Complex and Series of Mono-Oxo Molybdenum(IV) and Tungsten(IV) Complexes. Structural and Electronic Effects of π-Bonding in trans-[M(O)(X)(dppe)2]+/0 Systems

Ligand-Field Photolysis of [Mo(CN)8]4− in Aqueous Hydrazine: Trapped Mo(II) Intermediate and Catalytic Disproportionation of Hydrazine by Cyano-Ligated Mo(III,IV) Complexes

Oxocyano complexes of molybdenum(IV) and tungsten(IV) with Schiff base ligands derived from salicylaldehyde and aliphatic amines. Crystal structure of [PPh4]2[Mo(CN)3O(ensal)]·5.5H2O (Hensal = N-salicylideneethylenediamine)

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Synthesis and Characterization of a Stable trans-Dioxo Tungsten(IV) Complex and Series of Mono-Oxo Molybdenum(IV) and Tungsten(IV) Complexes. Structural and Electronic Effects of π-Bonding in trans-[M(O)(X)(dppe)₂]^+/0 Systems

Synthesis and Characterization of a Stable trans-Dioxo Tungsten(IV) Complex and Series of Mono-Oxo Molybdenum(IV) and Tungsten(IV) Complexes. Structural and Electronic Effects of π-Bonding in trans-[M(O)(X)(dppe)₂]^+/0 Systems

Ligand-Field Photolysis of [Mo(CN)₈]⁴⁻ in Aqueous Hydrazine: Trapped Mo(II) Intermediate and Catalytic Disproportionation of Hydrazine by Cyano-Ligated Mo(III,IV) Complexes