Electrophilic “Fischer Type” Phosphinidene Complexes of Molybdenum, Tungsten, and Ruthenium

Sterenberg, Brian T.; Udachin, and Konstantin A.; Carty, Arthur J.

doi:10.1021/om010225y

Cited by 79 publications

(59 citation statements)

References 28 publications

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“…Their insertion into s bonds, addition to p bonds, and coordination to lone pairs is well-documented and reviewed. [1,8] More diversity in ancillary ligands is available in cationic complexes [L n M = P À R] + , of which stable ones [17] with limited reactivity have been reported.…”

Section: Transition-metal Ligationmentioning

confidence: 99%

Nucleophilic Phosphinidene Complexes: Access and Applicability

2010

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Syntheses, properties, and reactivities of nucleophilic phosphinidene complexes [L(n)M=P-R] are reviewed. Emphasis is placed on the electronic tuning of this emerging class of phosphorus reagents, using different ancillary ligands and coordinatively unsaturated transition-metal moieties. The difference in applicability of the established stable 18-electron and transient 16-electron phosphinidenes is addressed.

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Section: Transition-metal Ligationmentioning

confidence: 99%

Nucleophilic Phosphinidene Complexes: Access and Applicability

2010

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“…The electrophilic complexes prepared by Carty et al (e.g. 18) [140] are characterized by the presence of a positive charge which is delocalized between the metal and the phosphorus atoms. The amino substituent provides additional stabilization for the electrophilic phosphorus atom.…”

Section: The Nucleophilic Complexesmentioning

confidence: 99%

Phospha‐Organic Chemistry: Panorama and Perspectives

2003

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Since the beginning of the seventies, organophosphorus chemistry has been completely rejuvenated by the discovery of stable derivatives in which phosphorus has the coordination numbers one or two. The chemistry of these compounds mimics the chemistry of their all-carbon analogues. In this Review article this analogy is discussed for the phosphorus counterparts of alkenes, alkynes, and carbenes. In each case, the synthesis, reactivity, and coordination modes are briefly examined. Some special electronic configurations are also discussed, which include one-electron Pbond;P bonds, strained bonds, and aromatic systems. To conclude, some potential applications of this chemistry in the areas of molecular materials and homogeneous catalysis are presented.

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“…38 Over the past few years we have isolated a series of cationic, terminal complexes including the remaining member [Cp*Cr(CO) 3 -{PN 21,[23][24][25]34 These molecules, all of which have been structurally characterized, display several important features. They are thermally stable, despite in some notable cases, such as the Re and Co compounds, the lack of sterically encumbered substituents on the metal or phosphorus ligand.…”

Section: ' Introductionmentioning

confidence: 99%

Synthesis and Structural Characterization of the First Thermally Stable, Neutral, and Electrophilic Phosphinidene Complexes of Vanadium

et al. 2011

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The first thermally stable, neutral, electrophilic phosphinidene complexes of vanadium, [CpV(CO)3{η1-P(NR2)}] (R = i Pr (3a), Cy (3b)), have been prepared by the reaction of [Na]2[CpV(CO)3] with Cl2PNR2. The molecules 3a and 3b have been characterized by microanalysis, IR, and 1H and 31P{1H} NMR spectroscopy, and for 3a also by single-crystal X-ray diffraction. The structure of 3a exhibits a piano stool geometry closely related to that of CpV(CO)4 with an η1-phosphinidene ligand replacing CO in one of the basal coordination sites of the vanadium atom (V(1)−P(1) = 2.300(2) Å). The reactivity of 3a toward a variety of unsaturated substrates: PhCCPh, di- t Bu-imidazol-2-ydene, PhN3, and Ph2CNN has been examined to probe the electrophilic (or nucleophilic) character of the low-coordinate P(I) site. In all cases reactions occur exclusively at the phosphinidene phosphorus atom, without CO displacement, affording examples of P-coordinated phosphirene [CpV(CO)3{P(N i Pr2)CPhCPh}] (7), abnormal NCN carbene adduct [CpV(CO)3{P(N i Pr2)-4-cyclo-C3H2-1,3-(N t Bu)2)}] (8), diazaphosphaimine [CpV(CO)3{P(N i Pr2)N−NCPh2}] (12), and P-coordinated phosphaimine [CpV(CO)3{P(N i Pr2)NPh}] (14) complexes. The η1-phosphaimine complexes 12 and 14 lose carbon monoxide to yield derivatives [CpV(CO)2{P(N i Pr2)N−NCPh2}] (9) and [CpV(CO)2{P(N i Pr2)NPh}] (15), which contain η2-(P,N)-coordinated phosphaimine ligands. An η3-(P,N,N)-bound phosphaimine ligand is present in an isomer of 9, namely, [CpV(CO)2{P(N i Pr2)N−NCPh2}], 13. Complexes 3a, 7, 8, 9, 14, and 15 have been characterized by X-ray crystallography.

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Electrophilic “Fischer Type” Phosphinidene Complexes of Molybdenum, Tungsten, and Ruthenium

Cited by 79 publications

References 28 publications

Nucleophilic Phosphinidene Complexes: Access and Applicability

Nucleophilic Phosphinidene Complexes: Access and Applicability

Phospha‐Organic Chemistry: Panorama and Perspectives

Synthesis and Structural Characterization of the First Thermally Stable, Neutral, and Electrophilic Phosphinidene Complexes of Vanadium

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