Dioxododecaisopropoxytetratungsten. Oxygen atom abstraction from acetone in reactions with hexaisopropoxyditungsten (WW)

Blatchford, Timothy P.; Chisholm, Malcolm H.; Folting, Kirsten; Huffman, John C.

doi:10.1039/c39840001295

Cited by 17 publications

(6 citation statements)

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“…The W2(0-i-Pr)6(py)2 compound with a tungsten-tungsten triple bond has been shown to couple acetone to 2,3-dimethyl-2-butene with the resulting formation of W402(0-i-Pr)12. 80 The tungsten complex here effects the oxygen extrusion from acetone, but the exact mechanism is not clear. plex, which has been structurally characterized, is an excellent model for the postulated intermediate in the reactions of McMurry (although the heterogeneous titanium systems may not contain metal-metal bonds).…”

Section: B Zirconium and Hafniummentioning

confidence: 98%

Carbonyl coupling reactions using transition metals, lanthanides, and actinides

Kahn¹,

Rieke²

1988

Chem. Rev.

203

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Section: B Zirconium and Hafniummentioning

confidence: 98%

Carbonyl coupling reactions using transition metals, lanthanides, and actinides

Kahn¹,

Rieke²

1988

Chem. Rev.

203

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“…Wiberg found E (P=C)=+3.0 kJ/mol at the MP2(fc)/6‐31+G(d) level [77] . Schoeller has apparently calculated the Z (P=C) form in a communication, but no details are provided [78,79] . In more recent work, Schoeller has only considered the E (P=C) isomer [80] as has Chernega [81] .…”

Section: Resultsmentioning

confidence: 99%

Are Monophospha(III)amidines and ‐guanidines with Ionizable Hydrogens Tautomeric? Towards a Deeper Understanding of Two Related Hetero‐element Functional Groups

Masuda,

Mokhtabad Amrei,

Boeré

2023

Eur J Inorg Chem

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This paper presents definitive structural evidence for N,P(III)‐monophosphaamidines in P=C and N=C isomeric forms from a combination of new syntheses, single‐crystal X‐ray diffraction (SC‐XRD), solid‐state NMR and FTIR. Evidence is also provided for C‐amino‐(σ2,λ3)‐phosphaalkene and C‐(σ3,λ3)‐phosphinoimine tautomerism in solution using multi‐nuclear NMR methods. Synthesis and SC‐XRD structure determination of a trisubstituted N,N’,P(III)‐monophosphaguanidine is presented, the first structure of a phospha(III)guanidine with two ionizable H atoms. The structural evidence is convincing for an N=C geometry, resulting in both N−H and P−H in the molecule. A detailed computational investigation using DFT methods is presented, with the goal of understanding the tautomeric structure preferences both at the fundamental level (parent molecules with all substituents on the heteroatoms being hydrogen) and using the full structures containing the very bulky 2,6‐diisopropylphenyl (Dipp) substituents employed in this study. Arguments are espoused for treating phospha(III)amidines and ‐guanidines as new types of functional groups, similar to but distinct from the familiar organic analogues. Limited reactivity studies and a voltammetry study of one phospha(III)amidine are included with the supporting information.

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“…In a chance reaction between W 2 (O i Pr) 6 (py) 2 and acetone‐d 6 in a NMR tube the black crystalline compound W 4 O 2 (O i Pr) 12 (py) was discovered 16. The source of the oxygen was traced to the acetone when, in a study of the protio species, we identified Me 2 C=CMe 2 as being the other product.…”

Section: Resultsmentioning

confidence: 99%

Factors influencing the reductive cleavage of C-X multiple bonds in their reactions with metal-metal multiple bonds (X = C, N, O, S)

Chisholm¹

2001

Chem. Record

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Though metal-metal multiple bonds of the transition elements are redox active, their reactivity towards C-X multiple bonds (X = C, N, O, S) vary greatly depending principally on: 1. The coordination geometry of the metal. 2. The oxidation state of the metal and the electronic configuration of the M-M bond. 3. The nature of the attendant ligands. Specific examples of C-X multiple bond activation at dimolybdenum and ditungsten centers are presented that illustrate the importance of these factors. Evidence is presented to support the view that reductive cleavage of a C-X multiple bond can be considered to be equivalent to an intramolecular redox reaction within a [M2CX] "cluster complex," for which the frontier orbital energies of the C-X and M-M multiple bonds are of paramount importance. Some applications of these C-X reductive cleavage reactions toward organic synthesis are described.

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Dioxododecaisopropoxytetratungsten. Oxygen atom abstraction from acetone in reactions with hexaisopropoxyditungsten (WW)

Cited by 17 publications

References 0 publications

Carbonyl coupling reactions using transition metals, lanthanides, and actinides

Carbonyl coupling reactions using transition metals, lanthanides, and actinides

Are Monophospha(III)amidines and ‐guanidines with Ionizable Hydrogens Tautomeric? Towards a Deeper Understanding of Two Related Hetero‐element Functional Groups

Factors influencing the reductive cleavage of C-X multiple bonds in their reactions with metal-metal multiple bonds (X = C, N, O, S)

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