The behaviour of trioxo(diethylenetriamine)molybdenum(VI) and trioxo(diethylenetriamine)tungsten(VI) in solution

Taylor, Roger S.; Gans, Paul; Knowles, P.; Sykes, A. G.

doi:10.1039/dt9720000024

Cited by 18 publications

(6 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It is possible that (Me 3 tach)MoO 3 undergoes hydrolysis in D 2 O to produce a solution containing molybdate ions (MoO 4 2- ). Similar observations were reported for the hydrolysis of the related (dien)MO 3 (M = Mo, W) complexes . Consistent with this possibility, the 95 Mo and 17 O NMR chemical shifts 31 for (Me 3 tach)MoO 3 in D 2 O solution (δ −2 and 536, respectively) are very close to those for Na 2 MoO 4 in D 2 O (δ 0 and 532 33 ).…”

Section: Resultssupporting

confidence: 85%

Oxidations of (R₃tach)M(CO)₃Complexes [M = Cr, Mo, W; R₃tach = 1,3,5-Trialkyl-1,3,5-triazacyclohexane (R =t-Bu, Bn)]. Crystal Structures of (t-Bu₃tach)MO₃·15H₂O (M = Mo, W)

et al. 1999

View full text Add to dashboard Cite

Stable Cr, Mo, and W complexes having a metal in oxidation state II, III, or VI, and possessing a facially coordinated 1,3,5-trialkyl-1,3,5-triazacyclohexane (R(3)tach) ligand, can be prepared by oxidation of (R(3)tach)M(CO)(3) with a variety of oxidizing agents. The reaction of the chromium or molybdenum complexes (R(3)tach)M(CO)(3) (M = Cr, R = Bn (benzyl), t-Bu and M = Mo, R = t-Bu) with bromine or thionyl chloride at reflux affords a series of monomeric M(III) trihalide complexes. More controlled oxidation of (t-Bu(3)tach)M(CO)(3) (M = Mo, W) with either bromine or iodine yields the 7-coordinate M(II) cations [(t-Bu(3)tach)M(CO)(3)X](+) (X = Br, I); protonation with trifluoromethanesulfonic acid affords the isolable [(t-Bu(3)tach)M(CO)(3)H](+) cations as their trifluoromethanesulfonate salts. Exhaustive oxidation of (t-Bu(3)tach)M(CO)(3) (M = Mo, W) with hydrogen peroxide affords the monomeric M(VI) trioxo complexes (t-Bu(3)tach)MO(3). The facial complexes (t-Bu(3)tach)MO(3) (M = Mo, W) have been characterized by room-temperature single-crystal X-ray diffraction studies. The complexes both crystallize with 15 waters of hydration and lie on the 3-axes of rhombohedral R3c cells of dimensions a = 21.026(3) Å and c = 13.418(2) Å for M = Mo and a = 21.011(3) Å and c = 13.390(3) Å for M = W. The array is a superlattice on a quasi-R3m structure (c halved) with successive molecules along c slightly staggered and with a small perturbation on the molecular symmetry, degrading it from 3m to 3. The Mo=O (W=O) bond distances are 1.724(3) Å (1.745(4) Å), and the Mo-N (W-N) bond distances are 2.374(3) Å (2.355(6) Å). The O-Mo-O (O-W-O) angles are 107.1(2) degrees (106.4(3) degrees ), and the N-Mo-N (N-W-N) angles are 58.8(1) degrees (59.0(3) degrees ). The high solvent component is associated with a hydrogen-bonded array, with the substrate molecules lying in axial tunnels in an ice-like structure.

show abstract

Section: Resultssupporting

confidence: 85%

Oxidations of (R₃tach)M(CO)₃Complexes [M = Cr, Mo, W; R₃tach = 1,3,5-Trialkyl-1,3,5-triazacyclohexane (R =t-Bu, Bn)]. Crystal Structures of (t-Bu₃tach)MO₃·15H₂O (M = Mo, W)

et al. 1999

View full text Add to dashboard Cite

show abstract

“…Our interest in the high-valent chemistry of tungsten and its role in biochemistry − has led to the discovery of a number of oxotungsten(VI) complexes containing the hydrotris(3,5-dimethylpyrazol-1-yl)borate ligand, L; − here, we report the synthesis and characterization of LW VI O 2 (OH), NEt 4 [LW VI O 3 ]·4H 2 O, and [LW VI O 2 ] 2 (μ-O), a tungsten L III -edge EXAFS study of LWO 2 (OH), NEt 4 [LWO 3 ]·4H 2 O, and related complexes, and the crystal structures of NEt 4 [LWO 3 ]·4H 2 O and [LWO 2 ] 2 (μ-O). Monomeric fac trioxotungsten(VI) complexes are rare and include [WO 3 S] 2- , (dien)WO 3 , [WO 3 (CH 2 CMe 3 )] - , (tcn)WO 3 and (Me 3 tcn)WO 3 , − [Cp*WO 3 ] - , , and [LWO 3 ] - − ,− …”

Section: Introductionmentioning

confidence: 99%

Oxotungsten(VI) Chemistry of Hydrotris(3,5-dimethylpyrazol-1-yl)borate: Hydroxodioxotungsten(VI), Trioxotungsten(VI), and (μ-Oxo)bis[dioxotungsten(VI)] Complexes

et al. 1997

View full text Add to dashboard Cite

Colorless, diamagnetic, air-stable LW VI O 2 (OH) [L ) hydrotris(3,5-dimethylpyrazol-1-yl)borate] forms when suspensions of LW II I(CO) 3 in dimethyl sulfoxide are heated at 100 °C. The complex was characterized by microanalysis, high-resolution mass spectrometry, and IR, NMR, and EXAFS spectroscopic techniques. The complex behaves as a weak acid with a pK a of around 4.7. Reaction of LWO 2 (OH) with NEt 4 OMe results in the formation of colorless, diamagnetic, air-stable NEt 4 [LW VI O 3 ], which crystallizes as a tetrahydrate. Crystals of NEt 4 [LWO 3 ]‚4H 2 O are monoclinic, space group P2 1 /c, with a ) 18.804(4) Å, b ) 9.901(8) Å, c ) 17.447(3) Å, β ) 104.35(2)°, and V ) 3146(1) Å 3 for Z ) 4. The structure is composed of discrete NEt 4 + and fac-[LWO 3 ]ions strung in an alternating fashion along both sides of a zigzag ladder of hydrogen-bonded water molecules (directed parallel to the b axis). The distorted-octahedral [LWO 3 ] -anions, with W-O(1) ) 1.740(4) Å, W-O(2) ) 1.759(4) Å, and W-O(3) ) 1.765(4) Å, are hydrogen-bonded to water molecules through two oxo groups, with WO(2)‚‚O(5) i ) 2.666(6) Å and WO(3)‚‚O(4) ii ) 2.693(6) Å. The EXAFS spectra of NEt 4 [LWO 3 ]‚4H 2 O and LWO 2 (OH) and related complexes are diagnostic of the respective trioxo or hydroxo-dioxo centers present. Colorless, diamagnetic, air-stable [LW VI O 2 ] 2 (µ-O) is produced in a number of reactions, including the oxidation of LW VI O 2 (µ-O)W IV O(CO)L and metathesis reactions involving LW VI O 2 Cl. The complex exhibits NMR spectra consistent with molecular C 2 symmetry and IR bands assignable to ν(WO 2 ) (945 and 900 cm -1 ) and ν as (WOW) (780 cm -1 ) vibrational modes. Crystals of [LW VI O 2 ] 2 (µ-O) are monoclinic, space group C2/c, with a ) 28.112-(7) Å, b ) 9.538(7) Å, c ) 15.722(8) Å, β ) 115.56(2)°, and V ) 3802(3) Å 3 for Z ) 4. The dinuclear structure is composed of distorted-octahedral LWO 2 units linked by the µ-oxo ligand; the terminal WdO bond lengths are identical at 1.715(5) Å, while the bridging W-O(3) distance is 1.893(1) Å.

show abstract

“…(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%

“…The perchlorate ligand in W(0C103)(CO)2(NO)(PPh3)2 ( 16) appears to be coordinated through a single oxygen atom. This complex is a useful precursor for other complexes of the type WX(CO)2(NO)(PPh3)2; the addition of a coordinating anion in acetone gives good yields of the 11). Every attempt to displace the C104~by CO, even under pressure, failed.…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

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

Hillhouse¹,

Haymore²

1987

Inorg. Chem.

View full text Add to dashboard Cite

The behaviour of trioxo(diethylenetriamine)molybdenum(VI) and trioxo(diethylenetriamine)tungsten(VI) in solution

Cited by 18 publications

References 0 publications

Oxidations of (R₃tach)M(CO)₃Complexes [M = Cr, Mo, W; R₃tach = 1,3,5-Trialkyl-1,3,5-triazacyclohexane (R =t-Bu, Bn)]. Crystal Structures of (t-Bu₃tach)MO₃·15H₂O (M = Mo, W)

Oxidations of (R₃tach)M(CO)₃Complexes [M = Cr, Mo, W; R₃tach = 1,3,5-Trialkyl-1,3,5-triazacyclohexane (R =t-Bu, Bn)]. Crystal Structures of (t-Bu₃tach)MO₃·15H₂O (M = Mo, W)

Oxotungsten(VI) Chemistry of Hydrotris(3,5-dimethylpyrazol-1-yl)borate: Hydroxodioxotungsten(VI), Trioxotungsten(VI), and (μ-Oxo)bis[dioxotungsten(VI)] Complexes

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

Contact Info

Product

Resources

About

The behaviour of trioxo(diethylenetriamine)molybdenum(VI) and trioxo(diethylenetriamine)tungsten(VI) in solution

Cited by 18 publications

References 0 publications

Oxidations of (R3tach)M(CO)3Complexes [M = Cr, Mo, W; R3tach = 1,3,5-Trialkyl-1,3,5-triazacyclohexane (R =t-Bu, Bn)]. Crystal Structures of (t-Bu3tach)MO3·15H2O (M = Mo, W)

Oxidations of (R3tach)M(CO)3Complexes [M = Cr, Mo, W; R3tach = 1,3,5-Trialkyl-1,3,5-triazacyclohexane (R =t-Bu, Bn)]. Crystal Structures of (t-Bu3tach)MO3·15H2O (M = Mo, W)

Oxotungsten(VI) Chemistry of Hydrotris(3,5-dimethylpyrazol-1-yl)borate: Hydroxodioxotungsten(VI), Trioxotungsten(VI), and (μ-Oxo)bis[dioxotungsten(VI)] Complexes

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

Contact Info

Product

Resources

About

Oxidations of (R₃tach)M(CO)₃Complexes [M = Cr, Mo, W; R₃tach = 1,3,5-Trialkyl-1,3,5-triazacyclohexane (R =t-Bu, Bn)]. Crystal Structures of (t-Bu₃tach)MO₃·15H₂O (M = Mo, W)

Oxidations of (R₃tach)M(CO)₃Complexes [M = Cr, Mo, W; R₃tach = 1,3,5-Trialkyl-1,3,5-triazacyclohexane (R =t-Bu, Bn)]. Crystal Structures of (t-Bu₃tach)MO₃·15H₂O (M = Mo, W)