Monomeric complexes of tungsten (0-VI) containing the ligand N,N',N"-trimethyl-1,4,7-triazacyclononane and their electrochemical properties. Preparation of [L2W2O5](PF6)2 and identification of its mixed-valence tungsten (VI)/tungsten(V) complex

Backes-Dahmann, G.; Wieghardt, Karl

doi:10.1021/ic00218a019

Cited by 34 publications

(17 citation statements)

References 2 publications

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“…(2-PF6) and carbon monoxide, as shown in eq 1. The ligand replacement reaction proceeds rapidly (10)(11)(12)(13)(14)(15)…”

Section: Resultsmentioning

confidence: 99%

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Syntheses and reactions of WH(CO)2(NO)(P(C6H5)3)2 and related tungsten nitrosyl complexes

Hillhouse¹,

Haymore²

1987

Inorg. Chem.

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“…(2-PF6) and carbon monoxide, as shown in eq 1. The ligand replacement reaction proceeds rapidly (10)(11)(12)(13)(14)(15)…”

Section: Resultsmentioning

confidence: 99%

“…As shown in eq 8, the reaction is reversible; when CO It is noteworthy that dimethyldithiocarbamate reacts with 2 in a different manner than the other anions previously discussed (Scheme III). The initial isolated product is a monophosphine, di-dicarbonyl complex, ds-W(CO)2(NO)(PPh3)(S2CNMe2) (13).…”

Section: Resultsmentioning

confidence: 99%

Syntheses and reactions of WH(CO)2(NO)(P(C6H5)3)2 and related tungsten nitrosyl complexes

Hillhouse¹,

Haymore²

1987

Inorg. Chem.

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“…6,7 Halogenation by iodine, 8 bromine, 9 and chlorine 10 is common in the literature. Oxidative decarboxylation with hydrofluoric acid 11 or addition of fluoride to a neutral tungsten(II) dicarbonyl complex 12 can provide access to the less common tungsten fluoride complexes. Despite decades of study, we are only aware of one literature report that includes the entire series of halocarbonyl tungsten complexes for a single ligand system, 11 and the hydridocarbonyl analogs of the halide complexes are seldom mentioned.…”

Section: Introductionmentioning

confidence: 99%

“…Oxidative decarboxylation with hydrofluoric acid 11 or addition of fluoride to a neutral tungsten(II) dicarbonyl complex 12 can provide access to the less common tungsten fluoride complexes. Despite decades of study, we are only aware of one literature report that includes the entire series of halocarbonyl tungsten complexes for a single ligand system, 11 and the hydridocarbonyl analogs of the halide complexes are seldom mentioned. Halocarbonyl complexes can be used as catalysts for wideranging reactions in homogeneous catalysis, 13,14 and they are also used as catalyst precursors for heterogeneous polymerization.…”

Section: Introductionmentioning

confidence: 99%

“…15 Chelating donor ligands anchor the coordination sphere of many seven-coordinate d 4 complexes with halide ligands. 11,[16][17][18][19][20] Phosphine-based pincer complexes have become popular due to their ability to sit at the pivot point of stability and reactivity in metal complexes. [21][22][23][24] Chelating phosphines are known to increase the basicity of the metal center, [25][26][27] and for tridentate ligands this donor behavior can also be affected by the bonding geometry adopted by the chelate.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and oxidation of d6 tungsten pincer complexes: a complete series of tungsten(ii) hydridocarbonyl and halocarbonyl pincer complexes

2012

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Reaction of the neutral P(H)NP ligand [HN(SiMe(2)CH(2)PPh(2))(2)] with tungsten hexacarbonyl resulted in coordination of P(H)NP through both phosphorus donor atoms to form the tungsten complex [W(P(HN)P)(CO)(4)] (1). Reaction of P(H)NP with tris(acetonitrile)tricarbonyl tungsten gave both facial and meridional tridentate isomers [W(P(H)NP)(CO)(3)] (2-fac and 3-mer). These three d(6) tungsten complexes could be interconverted under appropriate conditions. The thermodynamically favored isomer 3 was protonated to form seven-coordinate [W(P(H)NP)(CO)(3)H][BF(4)] (4). A related series of cationic tungsten(II) halide complexes was synthesized, [W(P(H)NP)(CO)(3)X](+) (6, X = I; 7, X = Br; 8, X = Cl; 9, X = F), by various routes. All of the tungsten(II) complexes underwent deprotonation at the amine site of the P(H)NP ligand when triethylamine was added, resulting in neutral seven-coordinate complexes. Variable temperature (1)H, (31)P{(1)H}, and (13)C{(1)H} NMR spectroscopy showed fluxional behavior for all the seven-coordinate complexes reported here. Analysis of IR and NMR spectroscopic data showed trends through the series of coordinated halides. Crystal structures of tetracarbonyl 1, meridional tricarbonyl 3, and cationic hydride 4 were determined to confirm the coordination mode of the P(H)NP ligand.

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Synthesis, Electrochemistry, and Oxygen-Atom Transfer Reactions of Dioxotungsten(VI) and -molybdenum(VI) Complexes with N2O2 and N2S2 Tetradentate Ligands

Wong

Fang

Law

et al. 1999

Eur. J. Inorg. Chem.

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A series of N2O2 tetradentate ligands with a range of substituents attached to the nitrogen atoms have been prepared (H2Ln) (n = 1–9). Treatment of these ligands and the N2S2 tetradentate ligand H2L10 with [WO2Cl2(DME)] (DME = 1,2‐dimethoxyethane) in the presence of triethylamine leads to the formation of cis‐dioxotungsten(VI) complexes [WO2(Ln)] (n = 1–10). Reaction of the N2O2 tetradentate ligands H2Ln (n = 1, 3–7) with ammonium molybdate tetrahydrate and dilute hydrochloric acid gives the corresponding molybdenum(VI) analogs [MoO2(Ln)] (n = 1, 3–7). These compounds have been spectroscopically characterized and the molecular structures of [WO2(Ln)] (n = 1, 2, 9) and [MoO2(L5)] have been established by X‐ray diffraction analysis. These high‐valent compounds participate in oxygen‐atom transfer reactions and can catalyze the oxidation of benzoin with dimethyl sulfoxide. The complex [WO2(L10)], which contains an S‐donor ligand, has lower reduction potential and higher reactivity toward oxo‐transfer reactions than analogous tungsten complexes having N2O2 ligands. The kinetics of these catalytic processes along with the structure and electrochemistry of these dioxotungsten and ‐molybdenum complexes are described and compared.

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Monomeric complexes of tungsten (0-VI) containing the ligand N,N',N"-trimethyl-1,4,7-triazacyclononane and their electrochemical properties. Preparation of [L2W2O5](PF6)2 and identification of its mixed-valence tungsten (VI)/tungsten(V) complex

Cited by 34 publications

References 2 publications

Syntheses and reactions of WH(CO)2(NO)(P(C6H5)3)2 and related tungsten nitrosyl complexes

Syntheses and reactions of WH(CO)2(NO)(P(C6H5)3)2 and related tungsten nitrosyl complexes

Synthesis and oxidation of d6 tungsten pincer complexes: a complete series of tungsten(ii) hydridocarbonyl and halocarbonyl pincer complexes

Synthesis, Electrochemistry, and Oxygen-Atom Transfer Reactions of Dioxotungsten(VI) and -molybdenum(VI) Complexes with N2O2 and N2S2 Tetradentate Ligands

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