Assembly of Molybdenum/Titanium μ-Oxo Complexes via Radical Alkoxide C−O Cleavage

Peters, Jonas C.; Johnson, Adam R.; Odom, Aaron L.; Wanandi, Paulus W.; Davis, W. M.; Cummins, Christopher C.

doi:10.1021/ja960564w

Cited by 69 publications

(73 citation statements)

References 109 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[5] In this methine (CH) transfer reaction, 7-chloronorbornadiene [25][26][27] is used as the methine source, while the three-coordinate titanium(iii) complex [Ti(NtBuAr) 3 ] is used as a specific chlorine-atom abstractor. It is well documented that [Ti(NtBuAr) 3 ] is potent for the one-electron reduction of metal oxo groups, [28,29] carbonyl groups, [30] metalhalogen bonds, [31] and carbon-halogen bonds. [30] For the latter two substrate types, and for chlorine in particular, formation of [ClTi(NtBuAr) 3 À is an anionic system, with nucleophilic properties that are enhanced accordingly by the presence of the negative charge, the synthesis and characterization of terminal ruthenium carbide complexes that are charge neutral is a recent development of great significance.…”

Section: Terminal Carbide Complexes: Methine Groupmentioning

confidence: 99%

Terminal, Anionic Carbide, Nitride, and Phosphide Transition‐Metal Complexes as Synthetic Entries to Low‐Coordinate Phosphorus Derivatives

Cummins

2006

Angew Chem Int Ed

Self Cite

View full text Add to dashboard Cite

Anionic terminal one‐atom nitride, phosphide, and carbide complexes are excellent starting materials for the synthesis of ligands containing low‐coordinate phosphorus centers in the protecting coordination sphere of the metal complex. Salt‐elimination reactions with chlorophosphanes lead to phosphaisocyanide, iminophosphinimide, and diorganophosphanylphosphinidene complexes in which the unusual phosphorus ligands are stabilized by coordination. X‐ray structure analyses and density‐functional calculations illuminate the bonding in these compounds.

show abstract

Section: Terminal Carbide Complexes: Methine Groupmentioning

confidence: 99%

Terminal, Anionic Carbide, Nitride, and Phosphide Transition‐Metal Complexes as Synthetic Entries to Low‐Coordinate Phosphorus Derivatives

Cummins

2006

Angew Chem Int Ed

Self Cite

View full text Add to dashboard Cite

show abstract

“…Formally, an alkyl radical in the periphery of a [MoO] or a [MoN] fragment, for example a tBu radical, is substituted by a titanium complex radical (Scheme 58). [244] The reaction of 76 with 77 leads in the first step to the mnitrido complex 78, which is stable at temperatures below À 30 8C and which isomerizes to 79 with the release of a tBu radical in a first-order reaction (Scheme 58). The addition of further 77 leads to 80 and decomposition products of the tBu radical where again a m-N intermediate can be observed.…”

Section: Reviewsmentioning

confidence: 99%

Highlights in the Renaissance of Amidometal Chemistry

Kempe¹

2000

Angewandte Chemie International Edition

271

View full text Add to dashboard Cite

Turning a disadvantage to an advantage: The rather disappointing reactivity of the metal - nitrogen bond in comparison to the metal - carbon bond resulted in the neglect of amidometal chemistry after its heyday at the end of the 1960s and beginning of the 1970s. Today it is precisely this disadvantage which is being applied through the use of amido ligands to produce inert complex fragments with well-defined reaction centers. In this way the chemistry of the early transition metals has been markedly enriched, and interesting alternatives to the classically regarded cyclopentadienyl ligands are now available.

show abstract

“…25,26 This ability to easily recycle the titanium-byproducts generates a closed cycle for the synthesis of trisubtituted phosphines from P 4 . One might begin to contemplate a catalytic cycle using this system, however, the reduction of XTi(N[ t Bu]Ar) 3 is slow and P 4 is itself suseptible to reduction to Na 3 P by Na/Hg amalgam under such conditions.…”

mentioning

confidence: 99%

Radical synthesis of trialkyl, triaryl, trisilyl and tristannyl phosphines from P4

Cossairt

Cummins

2010

New J. Chem.

Self Cite

View full text Add to dashboard Cite

A reaction scheme has been devised according to 3 RX + 3 Ti(III) + 0.25 P 4 → PR 3 + 3 XTi(IV) wherein RX = PhBr, CyBr, Me 3 SiI, or Ph 3 SnCl with contrasting results in the case of more hindered RX; the scheme accomplishes direct radical functionalization of white phosphorus without intermediacy of PCl 3 .It is known that P 4 , white phosphorus, has excellent properties as a trap for carboncentered radicals in solution and under the mild conditions that are typical for organic synthesis. The most prominent example of this was the demonstration that phosphonic acids may be prepared from corresponding carboxylic acids by way of O-acyl derivatives of N-hydroxy-2-thiopyridone (Barton PTOC esters). 1 The latter provide carbon centered radicals in an oxygen-initiated chain reaction, and these are consumed upon combination with P 4 as the critical P-C bond-forming event; upon oxidative workup, any remaining P-P bonds are cleaved and the phosphonic acid RP(O)(OH) 2 is the end product. 2 It is also known that P-P bonds other than those in P 4 may serve as traps for organic radicals. This has been shown by Sato et al. in a scheme for radical phosphination of organic halides wherein ArX serves as a source of Ar· which in turn attacks For our part, we have previously shown that the three-coordinate titanium(III) complex Ti(N[ t Bu]Ar) 3 (Ar = 3,5-C 6 H 3 Me 2 ), 1, is a potent halogen-atom abstractor, capable of abstracting X· (X = Cl, Br, or I) from various donor molecules at room temperature or below, in aprotic organic media (Figure 1). With the present work, we sought to develop

show abstract

Assembly of Molybdenum/Titanium μ-Oxo Complexes via Radical Alkoxide C−O Cleavage

Abstract: Positional parameters and B(eq) for 95025 Peters/CCC

Cited by 69 publications

References 109 publications

Terminal, Anionic Carbide, Nitride, and Phosphide Transition‐Metal Complexes as Synthetic Entries to Low‐Coordinate Phosphorus Derivatives

Terminal, Anionic Carbide, Nitride, and Phosphide Transition‐Metal Complexes as Synthetic Entries to Low‐Coordinate Phosphorus Derivatives

Highlights in the Renaissance of Amidometal Chemistry

Radical synthesis of trialkyl, triaryl, trisilyl and tristannyl phosphines from P4

Contact Info

Product

Resources

About