The crystal structures of [1,2-bis(diphenylphosphino)ethane]trichloro(η-cyclopentadienyl)niobium(IV) bistoluene solvate and μ-oxo-bis[aquatrichloro(η-methylcyclopentadienyl)niobium(V)]

Prout, Keith; Daran, Jean Claude

doi:10.1107/s056774087901089x

Cited by 17 publications

(7 citation statements)

References 10 publications

(11 reference statements)

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“…The Nb atom lies 0.5391 Å above the equatorial plane toward the Cp ring. Nb−Cl (equatorial) and Nb−P bond lengths are longer than those found in CpNbCl 3 dppe. , The structure compares very well with the structure of the zirconium(IV) analogue, [ i -Pr P 2 Cp]ZrCl 3 ( 1 ), which has a similar geometry and comparable bond lengths and angles . Selected bond lengths and bond angles are shown in Tables and .…”

Section: Resultssupporting

confidence: 54%

Preparation and Reactivity of Zirconium(III), Niobium(III), and Molybdenum(III) Complexes Stabilized by a Cyclopentadienyl Unit with Pendant Phosphine Donors

1999

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This paper deals with the organometallic chemistry of the trivalent second-row transition metals of groups 4−6, namely, Zr, Nb, and Mo, with the cyclopentadienyldiphosphine ligand [η5-C5H3-1,3-(SiMe2CH2PR2)2], abbreviated as [RP2Cp] (where R = i-Pr and Ph). The Zr(IV) complex [ i -PrP2Cp]ZrCl3 undergoes reduction with Na/Hg to form the trivalent Zr derivative, [ i -PrP2Cp]ZrCl2, which undergoes a metathetical reaction with MeMgBr to yield the monomethyl derivative [ i -PrP2Cp]Zr(CH3)Cl. The reaction of the Zr(III) complex [ i -PrP2Cp]ZrCl2 with excess carbon monoxide results in disproportionation to the Zr(IV) complex, [ i -PrP2Cp]ZrCl3, and the Zr(II) compound [ i -PrP2Cp]Zr(CO)2Cl. This reaction is reversible, and upon removal of CO the starting material, [ i -PrP2Cp]ZrCl2 is formed. The preparation of the diamagnetic Nb(III) complex [RP2Cp]NbCl2 is achieved by the reaction of NbCl3(DME) with [RP2Cp]Li. [RP2Cp]NbCl2 complexes react with excess CO to form the CO adducts whose solid-state structures have been determined. The Nb(IV) derivatives [RP2Cp]NbCl3 are formed via the reaction of [RP2Cp]NbCl2 with PbCl2. These complexes can also be produced when Nb(O)Cl3(THF)2 is allowed to react with excess [RP2Cp]Li. These Nb(IV) derivatives are ESR active, and their solid-state molecular structures show distorted octahedral geometries around the Nb center. MoCl3(THF)3 reacts with [RP2Cp]Li to generate the corresponding Mo(III) complexes [RP2Cp]MoCl2. These compounds are low-spin, paramagnetic complexes as evidenced by their ESR spectra.

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Section: Resultssupporting

confidence: 54%

Preparation and Reactivity of Zirconium(III), Niobium(III), and Molybdenum(III) Complexes Stabilized by a Cyclopentadienyl Unit with Pendant Phosphine Donors

1999

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“…3 435( 1 1) 3 774 ( 12) 3 079 (10) 259( 1 1) 1318 (12) 606 ( 11) methods, full-matrix least-squares refinement with anisotropic thermal parameters in the last cycles for all the non-hydrogen atoms; hydrogen atoms placed at their geometrically calculated positions and introduced in the final calculations with isotropic thermal parameters. Weighting scheme used in the last cycles:…”

mentioning

confidence: 99%

Notes. Synthesis and characterization of monocyclopentadienyl niobium derivatives. X-Ray crystal structure of di-µ-chloro-µ-oxo-bis[dichloro(η-trimethylsilylcyclo-pentadienyl)niobium(V)], [{Nb(η-C₅H₄SiMe₃)Cl₂}₂(µ-O)(µ-Cl)₂]

Andreu¹,

Jalón²,

Otero³

et al. 1987

J. Chem. Soc., Dalton Trans.

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“…The other parameters for the central 03WC2W03 moiety were taken from the structure of 1 and were idealized to D3d symmetry.14 On the left-hand side of Figure 3 we show the frontier orbitals of two (HO)3W fragments separated by ca. 5 A.…”

Section: Resultsmentioning

confidence: 99%

Structure and bonding of (.mu.-dicarbido)hexa-tert-butoxyditungsten, (tert-BuO)3W.tplbond.CC.tplbond.W(O-tert-Bu)3

Caulton¹,

Cayton²,

Chisholm³

et al. 1992

Organometallics

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The molecular structure of (~-B u O )~W~! -C = W ( O -~-B U )~(1) has been determined by single-crystal X-ray crystallography-at -171 "C. The com ound crystallizes with two toluene molecules in the triclinic system, space group P1, with a = 10.926 (7) B, b = 15.706 (12) A, c = 9.674 (6) A, a = 90.99 ( 5 ) O , B = 90.27 (4)O, y = 82.59 (5)O, V = 1646.1 A3, and 2 = 1. The two W(O-t-Bu), groups are arranged in the staggered conformation. The C-C bond length of 1.34 (3) A in the bridge WEC-CEW moiety parallels that in H-C=C-C=C-H (1.384 (2) A). The WEC bond length of 1.819 (16) A is somewhat longer than that in most tungsten alkylidyne complexes. The UV-visible spectrum of 1 in hexane shows five absorptions at 430 (2490 M-' cm-l), 354 (7590 M-' cm-' 1, 294 (11 300 M-' cm-'), 254 (27800 M-' cm-'), and 246 (26800 M-' cm-') nm. Cyclic voltammetry measurements in CH2C12 with n-Bu4NPF6 (n-Bu = CH3CH2CH2CH2) as the supporting electrolyte reveal two irreversible oxidations at 0.362 and 0.816 V vs a saturated calomel electrode (SCE) reference. A MO calculation employing the Fenske-Hall method on the model compound (H0)3WC2W(OH)3 indicates that the C2 ligand is both a strong *-donor and strong ?r-acceptor, which leads to an approach of the limiting valence bond description W&-C=W for the central moiety. A comparison is made with the established chemistry of linear bridged dinitrogen complexes.

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The crystal structures of [1,2-bis(diphenylphosphino)ethane]trichloro(η-cyclopentadienyl)niobium(IV) bistoluene solvate and μ-oxo-bis[aquatrichloro(η-methylcyclopentadienyl)niobium(V)]

Cited by 17 publications

References 10 publications

Preparation and Reactivity of Zirconium(III), Niobium(III), and Molybdenum(III) Complexes Stabilized by a Cyclopentadienyl Unit with Pendant Phosphine Donors

Preparation and Reactivity of Zirconium(III), Niobium(III), and Molybdenum(III) Complexes Stabilized by a Cyclopentadienyl Unit with Pendant Phosphine Donors

Notes. Synthesis and characterization of monocyclopentadienyl niobium derivatives. X-Ray crystal structure of di-µ-chloro-µ-oxo-bis[dichloro(η-trimethylsilylcyclo-pentadienyl)niobium(V)], [{Nb(η-C₅H₄SiMe₃)Cl₂}₂(µ-O)(µ-Cl)₂]

Structure and bonding of (.mu.-dicarbido)hexa-tert-butoxyditungsten, (tert-BuO)3W.tplbond.CC.tplbond.W(O-tert-Bu)3

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The crystal structures of [1,2-bis(diphenylphosphino)ethane]trichloro(η-cyclopentadienyl)niobium(IV) bistoluene solvate and μ-oxo-bis[aquatrichloro(η-methylcyclopentadienyl)niobium(V)]

Cited by 17 publications

References 10 publications

Preparation and Reactivity of Zirconium(III), Niobium(III), and Molybdenum(III) Complexes Stabilized by a Cyclopentadienyl Unit with Pendant Phosphine Donors

Preparation and Reactivity of Zirconium(III), Niobium(III), and Molybdenum(III) Complexes Stabilized by a Cyclopentadienyl Unit with Pendant Phosphine Donors

Notes. Synthesis and characterization of monocyclopentadienyl niobium derivatives. X-Ray crystal structure of di-µ-chloro-µ-oxo-bis[dichloro(η-trimethylsilylcyclo-pentadienyl)niobium(V)], [{Nb(η-C5H4SiMe3)Cl2}2(µ-O)(µ-Cl)2]

Structure and bonding of (.mu.-dicarbido)hexa-tert-butoxyditungsten, (tert-BuO)3W.tplbond.CC.tplbond.W(O-tert-Bu)3

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Notes. Synthesis and characterization of monocyclopentadienyl niobium derivatives. X-Ray crystal structure of di-µ-chloro-µ-oxo-bis[dichloro(η-trimethylsilylcyclo-pentadienyl)niobium(V)], [{Nb(η-C₅H₄SiMe₃)Cl₂}₂(µ-O)(µ-Cl)₂]