[Li(dime)2][W(CO)5I] as a novel synthon for the preparation of silyl, amino and organyl derivatives of pentacarbonyl tungsten (dime = diethylene glycol dimethyl ether)

Palitzsch, Wolfram; Böhme, Uwe; Roewer, Gerhard

doi:10.1039/a700215g

Cited by 18 publications

(11 citation statements)

References 8 publications

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“…In another examination of the accuracy of DFT defined bond lengths, a tungsten coordination compound was further investigated by calculating the W− I distance in [W(CO) 5 I] − , given that I − is isoelectronic with Xe and the structure has been determined by X-ray crystallography. 27 We find that the calculated W−I distance (2.950 Å) is in reasonable agreement with experimental value (2.871(2) Å).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Our determined W–Xe bond length is 0.30 Å longer compared to Au–Xe where the report stated short bond may be due to the fact that “ Gold is the most electronegative transition element known, in part due to the strong relativistic effect ” and may explain the large charge transfer. In another examination of the accuracy of DFT defined bond lengths, a tungsten coordination compound was further investigated by calculating the W–I distance in [W(CO) 5 I] − , given that I – is isoelectronic with Xe and the structure has been determined by X-ray crystallography . We find that the calculated W–I distance (2.950 Å) is in reasonable agreement with experimental value (2.871(2) Å).…”

Section: Resultsmentioning

confidence: 99%

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Monitoring the Formation and Reactivity of Organometallic Alkane and Fluoroalkane Complexes with Silanes and Xe Using Time-Resolved X-ray Absorption Fine Structure Spectroscopy

et al. 2019

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Complexes with weakly coordinating ligands are often formed in chemical reactions and can play key roles in determining the reactivity, particularly in catalytic reactions. Using time-resolved X-ray absorption fine structure (XAFS) spectroscopy in combination with time-resolved IR (TRIR) spectroscopy and tungsten hexacarbonyl, W(CO)6, we are able to structurally characterize the formation of an organometallic alkane complex, determine the W–C distances, and monitor the reactivity with silane to form an organometallic silane complex. Experiments in perfluorosolvents doped with xenon afford initially the corresponding solvated complex, which is sufficiently reactive in the presence of Xe that we can then observe the coordination of Xe to the metal center, providing a unique insight into the metal–xenon bonding. These results offer a step toward elucidating the structure, bonding, and chemical reactivity of transient species by X-ray absorption spectroscopy, which has sensitivity to small structural changes. The XAFS results indicate that the bond lengths of metal–alkane (W–H–C) bond in W(CO)5(heptane) as 3.07 (±0.06) Å, which is longer than the calculated W–C (2.86 Å) for binding of the primary C–H, but shorter than the calculated W–C (3.12 Å) for the secondary C–H. A statistical average of the calculated W–C alkane bond lengths is 3.02 Å, and comparison of this value indicates that the value derived from the XAFS measurements is averaged over coordination of all C–H bonds consistent with alkane chain walking. Photolysis of W(CO)6 in the presence of HSiBu3 allows the conversion of W(CO)5(heptane) to W(CO)5(HSiBu3) with an estimated W–Si distance of 3.20 (±0.03) Å. Time-resolved TRIR and XAFS experiments following photolysis of W(CO)6 in perfluoromethylcyclohexane (PFMCH) allows the characterization of W(CO)5(PFMCH) with a W–F distance of 2.65 (±0.06) Å, and doping PFMCH with Xe allows the characterization of W(CO)5Xe with a W–Xe bond length of 3.10 (±0.02) Å.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Monitoring the Formation and Reactivity of Organometallic Alkane and Fluoroalkane Complexes with Silanes and Xe Using Time-Resolved X-ray Absorption Fine Structure Spectroscopy

et al. 2019

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“…Compared with the Cr(CO) 5 I moiety in complex (1), the W(CO) 5 I fragment in complex (12) deviates markedly from exact C 4v symmetry. For example, the C( [3]. It is different from that in complex (1), there being no direct interaction between anions and cations in the crystal structure.…”

Section: Electrochemical Properties Of the Complexesmentioning

confidence: 87%

“…irradiation or heating [1]. Recently, some novel synthetic routes have been explored to obtain these [M(CO) 5 X] ) anion complexes [2,3], and they have also been found to be useful as starting materials for further reactions, for example, reactions with different nucleophilic reagents to substitute the halide [3][4][5], or further oxidation of the metal center [6,7]. The structural characteristics of the [M(CO) 5 X] ) anions have also been investigated, indicating that the anions have approximate C 4v symmetry [8][9][10][11].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, crystal structures and electrochemical properties of group 6 metal carbonyl anion complexes

Hong

Tang

Yang

et al. 2005

Transition Met Chem

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A series of [M(CO) 5 I] ) and [M 2 (CO) 10 I] ) anion complexes have been synthesized by the photochemical reaction of PhCH 2 N(CH 3 ) 3 I or FcCH 2 N(CH 3 ) 3 I (Fc ¼ ferrocenyl) with M(CO) 6 (M = Cr, Mo or W), and characterized by elemental analyses, i.r., 1 H-n.m.r. and 13 C-n.m.r. spectra in the case of the molybdenum and tungsten complexes. These complexes exhibit considerably different electrochemical behavior, when investigated by cyclic voltammetry. The crystal structures of [PhCH 2 N(CH 3 ) 3 ][Cr(CO) 5 I] and [FcCH 2 N(CH 3 ) 3 ][W 2 (CO) 10 I] have been determined by X-ray diffraction, indicating that only weak contacts maybe exist between anions and cations by the IÁ Á ÁH bond in the former, and there are no direct interactions between anions and cations in the latter.

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“…For this reason, the design of such compounds seems to be very important. We have synthesized previously stable iodopentacarbonylmetalate complexes of molybdenum and tungsten . However, the chemistry of ionic transition-metal silyl derivatives is not very well explored.…”

Section: Introductionmentioning

confidence: 99%

First Crystal Structure of a Cyclohexasilyl Transition-Metal Derivative, [(DIME)₂Li][Mo(CO)₅Si₆Me₁₁] (DIME = Diethylene Glycol Dimethyl Ether)

et al. 1998

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[Li(dime)2][W(CO)5I] as a novel synthon for the preparation of silyl, amino and organyl derivatives of pentacarbonyl tungsten (dime = diethylene glycol dimethyl ether)

Cited by 18 publications

References 8 publications

Monitoring the Formation and Reactivity of Organometallic Alkane and Fluoroalkane Complexes with Silanes and Xe Using Time-Resolved X-ray Absorption Fine Structure Spectroscopy

Monitoring the Formation and Reactivity of Organometallic Alkane and Fluoroalkane Complexes with Silanes and Xe Using Time-Resolved X-ray Absorption Fine Structure Spectroscopy

Synthesis, crystal structures and electrochemical properties of group 6 metal carbonyl anion complexes

First Crystal Structure of a Cyclohexasilyl Transition-Metal Derivative, [(DIME)₂Li][Mo(CO)₅Si₆Me₁₁] (DIME = Diethylene Glycol Dimethyl Ether)

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[Li(dime)2][W(CO)5I] as a novel synthon for the preparation of silyl, amino and organyl derivatives of pentacarbonyl tungsten (dime = diethylene glycol dimethyl ether)

Cited by 18 publications

References 8 publications

Monitoring the Formation and Reactivity of Organometallic Alkane and Fluoroalkane Complexes with Silanes and Xe Using Time-Resolved X-ray Absorption Fine Structure Spectroscopy

Monitoring the Formation and Reactivity of Organometallic Alkane and Fluoroalkane Complexes with Silanes and Xe Using Time-Resolved X-ray Absorption Fine Structure Spectroscopy

Synthesis, crystal structures and electrochemical properties of group 6 metal carbonyl anion complexes

First Crystal Structure of a Cyclohexasilyl Transition-Metal Derivative, [(DIME)2Li][Mo(CO)5Si6Me11] (DIME = Diethylene Glycol Dimethyl Ether)

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First Crystal Structure of a Cyclohexasilyl Transition-Metal Derivative, [(DIME)₂Li][Mo(CO)₅Si₆Me₁₁] (DIME = Diethylene Glycol Dimethyl Ether)