Transformation of μ4-Phosphinidenes at an Ru5 Center:  Isolation and Structural Characterization of Hydroxyphosphinidene Cluster Acids, Fluorophosphinidenes, and a Novel μ5-Phosphide

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

doi:10.1021/ic040077e

Cited by 11 publications

(11 citation statements)

References 29 publications

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“…(iv) Like metal-carbene complexes, phosphinidene analogues have considerable potential in phosphaorganic synthesis and catalytic chemistry. 4 Our own interest in terminal phosphinidene complexes was stimulated by a longstanding interest in chemical transformations at bridging, μ-PR ligands in clusters 32,33 and by the discovery in 2001 of a synthetic route to isolable, cationic, terminal phosphinidene complexes of molybdenum and tungsten, [Cp*M(CO) 3 34 At the time these were the first fully characterized, electrophilic, terminal phosphinidene complexes, although NMR spectroscopic evidence had been reported 35 for a related iron cation, [Cp*Fe(CO) 2 …”

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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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 study of transition metal clusters has been an active area of current chemical research [1][2][3][4][5][6][7][8]. Discrete, soluble metal clusters often display catalytic activity and are studied as models for the surface of bulk metals [9,10].…”

Section: Introductionmentioning

confidence: 99%

Complexation and metallation of Ph2PCC(CH2)5CCPh2 in triosmium carbonyl clusters

Shiue¹,

Yeh²,

Lee³

et al. 2007

Journal of Organometallic Chemistry

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“…13 Reaction of Pd 10 (CO) 12 (PEt 3 ) 6 with Pd 2 (dba) 3 (dba = dibenzylideneacetone) or [Pd(NCMe) 4 ] 2+ affords Pd 52 (CO) 36 (PEt 3 ) 14 (ca. 5%) or Pd 66 (CO) 45 (PEt 3 ) 16 (13%), respectively. The clusters can be considered to be derived from a common Pd 38 core via condensation of Pd 7 caps and form mixed ccp/hcp layered structures.…”

Section: Homonuclear High-nuclearity Clustersmentioning

confidence: 99%

“…44 The m 5 -phosphido cluster 26 has been isolated from reaction of Ru 5 (m 4 -PNPr i 2 )-(m-dppm)(CO) 13 and HCl. 45 The heterodentate ligand 2,2 0 -bis(diphenylphosphino)-4,4 0 -bipyridine has been used to prepare a series of linked-cluster assemblies, including 27, where [Ir 4 Br(CO) 11 ] À was used as the core unit. 46 Ru 6 (m 6 -C)-(m-CO)(CO) 16 reacts with GaCp * to give air-sensitive Ru 6 (m 6 -C)(m 3 -GaCp * ) 2 -(m-GaCp * )(m-CO)(CO) 13 , and the structure of Rh 6 (m 3 -GaCp * ) 4 (CO) 12 has been reported.…”

Section: Reaction Of Ru 3 (M 3 -H) 2 (M-h) 3 Cp *mentioning

confidence: 99%

Organo‐Transition‐Metal Cluster Complexes

Humphrey

Cifuentes

2004

ChemInform

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This chapter covers the chemistry of metal carbonyl and organometallic clusters containing three or more metal atoms. The treatment is in Periodic Group order, homometallic compounds being followed by heterometallic clusters. Ligands are not shown for high-nuclearity clusters, emphasis being placed on core geometry. 2 Spectroscopic studies The first gas-phase infrared spectra of a range of anionic iron clusters ([Fe 3 (CO) 10 ] À to [Fe 5 (CO) 14 ] À) have been reported. Spectral data of this type were combined with DFT calculations for smaller complexes ([Fe(CO) 4 ] À , [Fe 2 (CO) 7 ] À , [Fe 2 (CO) 8 ] À) to obtain structural information for the cluster anions. 1 Spectroelectrochemical and computational studies on the reversible two-electron reduction of bis(alkynyl) clusters Ru 4 (m 4-Z 2-RC 2 R) 2 (m-CO)(CO) 10 show the first-formed product, which contains a square-planar metal core with the alkyne ligands coordinated to opposite faces, quickly isomerizes to a thermodynamically more stable product where the alkyne ligands lie parallel to each other across the metal framework. 2 Quantitative IR analysis of Rh 4 (m-CO) 3 (CO) 9 , combined with deconvolution techniques, has been used to obtain a spectrum of the all-terminal CO complex Rh 4 (CO) 12 , even though it constitutes only ca. 1% of the sample. 3 Laser desorption time-of-flight mass spectrometry affords the best results for anionic clusters when they are examined in the absence of matrix, the parent ion being observed in the majority of cases. In contrast, the spectra of neutral clusters show high-mass cluster aggregation and decarbonylation, with the CO:M ratio dropping with increasing cluster size, suggesting a metal-core rearrangement. 4 A picosecond time-resolved UV/Vis and IR spectroscopic study of the photolysis of Os 3 (CO) 10 (s-cis-cyclohexa-1,3-diene), combined with DFT calculations on the geometry-optimized Os 3 (CO) 10 (buta-1,3-diene), indicates products result from stepwise formation of two bridging carbonyl ligands, with each intermediate containing a cleaved Os-Os bond bridged by the 1,3-diene ligand. 5 Similar comparisons of the photochemical reactivity of the diimine clusters Os 3 (CO) 10 (Z-L) (L = [AcPy-MV] 2+ , Pr i-AcPy, 1) show that irradiation of the methyl viologen cluster results in transfer of a cluster-core electron to the lowest p * orbital of the MV 2+ unit, resulting in formation of a charge-separated state that is stable in acetonitrile, but either decays to regenerate the starting cluster (88%) or forms stable open-core biradicals (12%) in acetone. Electrochemical reduction of the viologen cluster decreases the electron-accepting characteristics of the ligand such that irradiation results in formation of zwitterions analogous to those observed from the irradiation of related non-substituted Os 3 (CO) 10 (a-diimine) clusters. 6 The related mixed-metal cluster RuOs 2 (CO) 10 (Pr i-AcPy) contains the diimine ligand coordinated to the ruthenium atom and also produces biradical products on irradiation in weakly coordinating so...

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Transformation of μ₄-Phosphinidenes at an Ru₅ Center: Isolation and Structural Characterization of Hydroxyphosphinidene Cluster Acids, Fluorophosphinidenes, and a Novel μ₅-Phosphide

Cited by 11 publications

References 29 publications

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

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

Complexation and metallation of Ph2PCC(CH2)5CCPh2 in triosmium carbonyl clusters

Organo‐Transition‐Metal Cluster Complexes

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