Mononuclear cis-carbonyloxotungsten(IV) complexes of hydrotris(3,5-dimethyl-1-pyrazolyl)borate

Feng, Siyang; Li, Luan; White, Peter S.; Brookhart, Maurice; Templeton, Joseph L.; Young, Charles G.

doi:10.1021/ic00012a003

Cited by 34 publications

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“…Mono‐oxo carbonyl complexes of W IV and Mo IV reported by Mayer et al 1d,f,h,i. and Young et al 1a–c,e. as well as theoretical studies by Mingos and co‐workers1g highlight the importance of these complexes.…”

Section: Methodsmentioning

confidence: 90%

Concurrent Stabilization of π‐Donor and π‐Acceptor Ligands in Aromatized and Dearomatized Pincer [(PNN)Re(CO)(O)₂] Complexes

et al. 2014

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Aromatized cationic [(PNN)Re(π acid)(O)2](+) (1) and dearomatized neutral [(PNN*)Re(π acid)(O)2] (2) complexes (where π acid=CO (a), tBuNC (b), or (2,6-Me2)PhNC (c)), possessing both π-donor and π-acceptor ligands, have been synthesized and fully characterized. Reaction of [(PNN)Re(O)2](+) (4) with lithiumhexamethyldisilazide (LiHMDS) yield the dearomatized [(PNN*)Re(O)2] (3). Complexes 1 and 2 are prepared from the reaction of 4 and 3, respectively, with CO or isocyanides. Single-crystal X-ray structures of 1 a and 1 b show the expected trans-dioxo structure, in which the oxo ligands occupy the axial positions and the π-acidic ligand occupies the equatorial plane in an overall octahedral geometry about the rhenium(V) center. DFT studies revealed the stability of complexes 1 and 2 arises from a π-backbonding interaction between the d(xy) orbital of rhenium, the π orbital of the oxo ligands, and the π* orbital of CO/isocyanide.

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Section: Methodsmentioning

confidence: 90%

Concurrent Stabilization of π‐Donor and π‐Acceptor Ligands in Aromatized and Dearomatized Pincer [(PNN)Re(CO)(O)₂] Complexes

et al. 2014

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“…The generation of LWOX(CO) and CO 2 upon reaction of LWI-(CO) 3 with O 2 at room temperature provides a precedent for the first of the two stepwise oxidations implied by eq 2. 47 Finally, LWO 2 (OH) was formed upon hydrolysis of LWO 2 -(SePh) 18 in acetonitrile according to eq 3, a reaction enhanced a Coordination number N, interatomic distance R (Å), and (thermal and static) mean-square deviation in R (the Debye-Waller factor) σ 2 (Å 2 ). The values in parentheses are estimated standard deviations (precisions) obtained from the diagonal elements of the covariance matrix.…”

Section: Resultsmentioning

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

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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.

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“…The synthesis and reactivity of complexes containing electronically disparate ligands, e.g. strong π-acids and π-bases, have attracted growing attention. − This communication describes the synthesis, characterization, and reactivity of carbonyl(η 2 -nitrile)tungsten(II), carbonyloxotungsten(IV), and carbonylthiotungsten(IV) complexes ( A − C ; L = hydrotris(3,5-dimethylpyrazol-1-yl)borate, X = monoanion) which combine π-acid carbonyl and π-base nitrile or chalcogenido ligands at a common metal center. These novel complexes have emerged from the development of a low-valent synthetic approach to bis(chalcogenido)tungsten(VI) complexes which involves successive two-electron-oxidation/atom-transfer reactions, beginning with [LW 0 (CO) 3 ] - , and progressing through LW II X(CO) x ( x = 2, 3), 5,9-12 LW II X(η 2 -RCN)(CO) (R = Me, Et, Ph), and LW IV EX(CO) (E = O, S) to LW VI E 2 X. , Quality (non-disordered) crystal structures of LW II (S 2 PR* 2 -S )(η 2 -MeCN)(CO) (R* = (−)-mentholate), LW IV O(S 2 PPh 2 -S )(CO), and LW IV S(S 2 PPh 2 -S )(CO) confirm the formulations and provide the first definitive metrical data for the metal cores in A − C , the structure of LW IV S(S 2 PPh 2 )(CO) being the first reported for any carbonylthiometal complex.…”

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Synthesis, Structures, and Reactivity of Four-Electron-Donor η²-Organonitrile, Carbonyl Oxo, and Carbonyl Thio Complexes of Tungsten

1996

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Reactions of LW(S2PR2)(CO)2 (L = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with pyridine N-oxide produce carbonyl oxo complexes, LWIVO(S2PR2)(CO). Thermal decarbonylation of LWX(CO)2 (X = halide) complexes in organonitrile solvents produces 4-electron-donor nitrile complexes, LWIIX(η2-RCN)(CO), which react with NH4[S2PR2] to form LWII(S2PR2)(η2-RCN)(CO). Reactions of the nitrile complexes with propylene sulfide result in high yields of the carbonyl thio complexes LWIVSX(CO) or LWIVS(S2PR2)(CO). The structures of LWIVO(S2PPh2)(CO), (R)-LWII(S2PR*2)(η2-MeCN)(CO) (R* = (−)-mentholate), and LWIVS(S2PPh2)(CO) can be rationalized in terms of the π-bonding requirements of the electronically disparate π-acid and π-base ligands.

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Mononuclear cis-carbonyloxotungsten(IV) complexes of hydrotris(3,5-dimethyl-1-pyrazolyl)borate

Cited by 34 publications

References 3 publications

Concurrent Stabilization of π‐Donor and π‐Acceptor Ligands in Aromatized and Dearomatized Pincer [(PNN)Re(CO)(O)₂] Complexes

Concurrent Stabilization of π‐Donor and π‐Acceptor Ligands in Aromatized and Dearomatized Pincer [(PNN)Re(CO)(O)₂] Complexes

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

Synthesis, Structures, and Reactivity of Four-Electron-Donor η²-Organonitrile, Carbonyl Oxo, and Carbonyl Thio Complexes of Tungsten

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Mononuclear cis-carbonyloxotungsten(IV) complexes of hydrotris(3,5-dimethyl-1-pyrazolyl)borate

Cited by 34 publications

References 3 publications

Concurrent Stabilization of π‐Donor and π‐Acceptor Ligands in Aromatized and Dearomatized Pincer [(PNN)Re(CO)(O)2] Complexes

Concurrent Stabilization of π‐Donor and π‐Acceptor Ligands in Aromatized and Dearomatized Pincer [(PNN)Re(CO)(O)2] Complexes

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

Synthesis, Structures, and Reactivity of Four-Electron-Donor η2-Organonitrile, Carbonyl Oxo, and Carbonyl Thio Complexes of Tungsten

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Concurrent Stabilization of π‐Donor and π‐Acceptor Ligands in Aromatized and Dearomatized Pincer [(PNN)Re(CO)(O)₂] Complexes

Concurrent Stabilization of π‐Donor and π‐Acceptor Ligands in Aromatized and Dearomatized Pincer [(PNN)Re(CO)(O)₂] Complexes

Synthesis, Structures, and Reactivity of Four-Electron-Donor η²-Organonitrile, Carbonyl Oxo, and Carbonyl Thio Complexes of Tungsten