A terminal molybdenum carbide prepared by methylidyne deprotonation

Peters, Jonas C.; Odom, Aaron L.; Cummins, Christopher C.

doi:10.1039/a704251e

Cited by 160 publications

(216 citation statements)

References 23 publications

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Section: Terminal Carbide Complexes: Methine Groupmentioning

confidence: 99%

“…[4] A one-pot synthesis has been developed for a high-yield conversion of [Mo(NtBuAr) 3 ] into its methylidyne counterpart (Scheme 2). [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.…”

Section: Terminal Carbide Complexes: Methine Groupmentioning

confidence: 99%

“…[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%

“…While the metal-ligand multiple-bond chemistry of singleatom ligands to date has featured most prominently the terminal oxo and nitrido functional groups, [1] recent developments have added terminal carbide [2][3][4][5][6][7][8] and phosphide [9][10][11][12][13][14][15][16][17][18] (alternatively carbido, phosphido) functional groups to the list of such available units. Terminal arsenic complexes were added to this list through the independent contributions of Schrock and Scheer.…”

Section: Introductionmentioning

confidence: 99%

“…Terminal arsenic complexes were added to this list through the independent contributions of Schrock and Scheer. [9,14] The outer limit so far for triple bonds between trivalent Group 6 metal fragments and heavier Group 15 3 . [19] Introduced herein is the idea that terminal, single-atom ligands constitute an attractive platform for the synthetic building up of interesting or unusual ligands within the protective coordination sphere of a metal complex.…”

Section: Introductionmentioning

confidence: 99%

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

Cummins

2006

Angew Chem Int Ed

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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.

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Section: Terminal Carbide Complexes: Methine Groupmentioning

confidence: 99%

Section: Terminal Carbide Complexes: Methine Groupmentioning

confidence: 99%

Section: Terminal Carbide Complexes: Methine Groupmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

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

Cummins

2006

Angew Chem Int Ed

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Highlights der Renaissance der Amidometallchemie

Kempe¹

2000

Angewandte Chemie

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Den vermeintlichen Nachteil nutzen: Die eher enttäuschende Reaktivität der Metall‐Stickstoff‐Bindung im Vergleich zur Metall‐Kohlenstoff‐Bindung ließ die Amidometallchemie nach ihrer Blüte Ende der sechziger, Anfang der siebziger Jahre etwas in Vergessenheit geraten. Heute nutzt man genau diesen Nachteil, um durch Amidoliganden inerte Komplexfragmente mit wohldefinierten Reaktionszentren zu bilden. Dadurch wurde die Chemie der frühen Übergangsmetalle bereichert, und neben den als klassisch anzusehenden Cyclopentadienylliganden stehen interessante Alternativen zur Verfügung.

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Alkyne Metathesis: Development of a Novel Molybdenum-Based Catalyst System and Its Application to the Total Synthesis of Epothilone A and C

2001

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Sterically hindered molybdenum(III) amido complexes of the general type [Mo[(tBu)(Ar)N]3] (1), upon treatment with CH2Cl2 or other halogen donors, have been converted into highly effective catalysts for all kinds of alkyne metathesis reactions. Although the actual nature of the propagating species formed in situ is still elusive, halogen transfer to the Mo center of 1 plays a decisive role in the activation of such precatalysts. It was possible to isolate and characterize by X-ray crystallography some of the resulting molybdenum halide derivatives such as 15, 16 and 20 which themselves were shown to be catalytically active. Numerous applications illustrate the performance of the catalytic system 1/CH2Cl2 which operates under mild conditions and tolerates an array of polar functional groups. The wide scope allows the method to be implemented into the total synthesis of sensitive and polyfunctional natural products. Most notable among them is a concise entry into the potent anticancer agents epothilone A (86) and C (88). The macrolide core of these targets is forged by ring closing alkyne metathesis (RCAM) of diyne 113, followed by Lindlar hydrogenation of cycloalkyne 114 thus formed. Since this strategy opens a stereoselective entry into (Z)-alkene 115, the approach is inherently more efficient than previous syntheses based on conventional RCM.

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A terminal molybdenum carbide prepared by methylidyne deprotonation

Cited by 160 publications

References 23 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 der Renaissance der Amidometallchemie

Alkyne Metathesis: Development of a Novel Molybdenum-Based Catalyst System and Its Application to the Total Synthesis of Epothilone A and C

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