Seven-vertex phosphinohalometallacarboranes of iron, cobalt, and nickel: syntheses, structures, and reactions

Boyter, Henry A.; Swisher, Robert G.; Sinn, Ekkehard; Grimes, Russell N.

doi:10.1021/ic00217a023

Cited by 39 publications

(18 citation statements)

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“…The dissociated Lewis base PPh 3 interacts with the boron, generating B−PPh 3 and Pd−H bonds. The formation of both B−H−M 3-7,14 interactions and B−PPh 3 bonds are well-documented in borane chemistry. The B−PPh 3 bond formation is always catalyzed by metals, and examples with Pd, Ni, and Pt have been reported .…”

Section: Discussionmentioning

confidence: 99%

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Formation of B−P Bonds through the Reaction of nido-Monophosphinocarboranes with Palladium(II) Complexes. The First Example of a Chelating R₂P−C−B−PR₂ Diphosphine

et al. 1999

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Reaction of [NMe4][7-PPh2-8-R-7,8-C2B9H10] (R = Me, H, Ph) with cis-[PdCl2(PPh3)2] in ethanol yielded [PdCl(7-PPh2-8-R-11-PPh2-7,8-C2B9H9)(PPh3)] (R = Me, H, Ph). The Pd(II) is in a square-planar arrangement. The carborane ligand chelates the Pd through two phosphorus atoms, one from C−PPh2 and the second from the generated B(11)−PPh2. The remaining two positions are filled by a PPh3 and one chloride. In the complexation process, a previously nonexistent B(11)−P bond is generated in the ligand. This is unambiguously demonstrated by a doublet in the 11B{1H} NMR spectrum and a 1:1:1:1 quartet in the 31P{1H} spectrum. The structure was fully elucidated by a crystal diffraction analysis of [PdCl(7-PPh2-8-Me-11-PPh2-7,8-C2B9H9)(PPh3)]·C7H8. By this reaction the hitherto unknown R2P−C−B−PPh2 chelating unit has been formed.

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Section: Discussionmentioning

confidence: 99%

“…The formation of both B−H−M 3-7,14 interactions and B−PPh 3 bonds are well-documented in borane chemistry. The B−PPh 3 bond formation is always catalyzed by metals, and examples with Pd, Ni, and Pt have been reported . The final step under these conditions is P−Ph bond cleavage from the PPh 3 group, in the synthesis of 1 − 3 .…”

Section: Discussionmentioning

confidence: 99%

Formation of B−P Bonds through the Reaction of nido-Monophosphinocarboranes with Palladium(II) Complexes. The First Example of a Chelating R₂P−C−B−PR₂ Diphosphine

et al. 1999

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“…Reagent quantities and yields were as follows. For 27,177 mg (0.56 mmol) of 4, 122 mg (0.56 mmol) of l-phenyl-2,3,4,5-tetra- Synthesis of (PC4Me4)Co(Et2C2B3H3)Co(NC4Me4) (30). In apparatus C (Figure 3), flasks A and B were each charged with a 2-3-fold excess of KH in oil and washed with hexane to remove the oil.…”

Section: Methodsmentioning

confidence: 99%

“…Transition-metal sandwich complexes that combine aromatic hydrocarbon and small carborane (R2C2B3H:-, &C2B3H2-, R2C2B4H:-) ligands have opened the way to a rich and diverse chemistry that has been extensively developed over the past d e~a d e .~ Perhaps the most striking feature of this chemistry is the ability of these (PC4Me4)Co(Et&2BoHS)Ru(MeC6H4CHMe2) (28) (PC4MeO2Co&EOC2B~H8) (29) (PC4Me4)Co(Et&2B3H3)Co(NC4Me4) (30) 6.1 (148), 3.4 (138) 2.6 (156), 4.1 (155) interactions, owing to the dominant electron-donor base character of the ring nitrogen atom;8 consequently, metal-pyrrole and -pyrrolyl sandwich species are relatively rare.B Hence, the prospect that carborane ligands might promote metal-heterocycle *-interaction was intriguing. Further, we considered that the ring heteroatom(s) in carborane-stabilized complexes could serve as sites for attaching reactive functional groups and for linking monomeric units together in chains.…”

Section: Introductionmentioning

confidence: 99%

“…?5-PC4Me4)-Co(Et2C2B3H3)CoCp* ( 27); a cobalt-ruthenium analogue, (PC4Me4)Co(Et2C2B3H3)Ru(MeC6H4CHMe2) (28), was synthesized from the (MeC6H4CHMe2)Ru(Et2C2B3H4)" anion, CoCl2, and the PC4Me4" ion. Reactions of the (i/6-PC4Me4)Co(Et2C2B3H4)" anion (26") with CoCl2 and with PC4Me4" or NC4Me4" ions gave, respectively, a bis(phospholyl) triple-decker, (PC4Me4)2Co2(Et2C2B3H3) (29), and a phospholyl-pyrrolyl triple-decker, (PC4Me4)Co(El^C2B3H3)Co(NC4Me4) (30). All of the new doubleand triple-decker sandwich species were isolated via column and/or plate chromatography as crystalline solids or oils and were characterized via multinuclear NMR, IR, UV-visible, and mass spectra, supported by X-ray diffraction data on 9 (to be reported elsewhere) and 30.…”

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Organotransition-metal metallacarboranes. 21. Transition-metal sandwich complexes of heterocyclic ligands. Carborane-stabilized .eta.5-pyrrolyl and .eta.5-phospholyl double-decker and triple-decker compounds: synthesis, structure, and electrochemistry

Chase¹,

Bryan²,

Woode³

et al. 1991

Organometallics

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This paper reports the controlled synthesis, characterization, and study of a series of pyrrolyl-and phospholyl-containing transition-metal sandwich complexes stabilized by cyclic Et2C2B3H,1-' (n = 3,5) carborane units, including the f i t triple-decker complexes of N-or P-containing heterocychc ligands. The reaction of the nid~-Et&~B,H; ion with CoC12 and a dimethyl-or tetramethylpyrrolide ion in THF generated the sandwich complexes (q5-NC4Me2Ft&~(Et&2B4H4) (la/lb, R = Me, H) together with the corresponding "decapitated" species (q5-NC4Me2FQCo(Et&2B3H5) (2a/2b, R = Me, H); in each case, subsequent treatment of the mixture with TMEDA (tetramethylethylenediamine) generated pure 2a or 2b. The reaction of the cobaltacarborane anion Cp*Co(Et,C,B,I-&)-with CoCl, and a di-or tetramethylpyrrolide ion in THF yielded the dicobalt triple-deckers (q5-NC4Me2R2)Co(Et2C2B3H3)CoCp* (5a/5b, R = Me, H). Reaction of the cymene-ruthenium-carborane complex anion (MeC6H4CHMe,)Ru(Et&B3H4)-with C0C12 and a di-or tetramethylpyrrolide ion afforded the cobalt-ruthenium triple-decker complexes (q5-NC4Me2R2)Co-(Et2C2B3H3)Ru(q6-1,4-MeC6H4CHMe2) (8a/8b, R = Me, H). Treatment of the deprotonated anion of 2a with CoCl, and NC4Me4-gave the bis(pyrroly1) triple-decker complex (q5-NC4Me4),Coz(EtzC2B3H3) (9). Although 5a reacted with CH31 to give the N-methyl cationic derivative 12, similar treatment of the dimethylpyrrolyl species 5b resulted only in iodo substitution at the central boron atom, B(5). Attempts at nucleophilic substitution at the ring nitrogen on the triple-decker pyrrolyl complexes, via reactions with alkyl halides, gave only B-halo derivatives. However, treatment of the monopyrrolyl and bis(pyrroly1) triple-decker complexes 5a and 9 with BH,.THF formed N-BH3 and NJV'-(BH3)2 adducts. The phmpholyl analogue of l a was prepared via the reaction of the tetramethylphospholide anion with nido-Et2C2B4H5-and CoCl,, forming the desired species (q5-PC4Me4)Co(Et2C2B4H4) (25), which was readily converted to (q5-PC4Me4)Co(Et2C2B3H5) (26) via treatment with wet TMEDA. The cobaltacarborane anion Cp*Co-(EhC2B3H6)-underwent a similar reaction to give the phospholyl-containing triple-decker (q5-PC4Me4)-Co(Et,C2B,H3)CoCp* (27); a cobalt-ruthenium analogue, (PC,Me4)Co(Et&,B3H3)Ru(MeC6-H4CHMe2) (2% was synthesized from the (MeC6H4~HMe2)Ru(Et&2B3H4)-anion, CoCl,, and the PC4Me4 ion. Reactions of the (q5-PC4Me4)Co(Et2C2B3H4) anion (26-) with CoCl, and with PC4Me4-or NC4Me4-ions gave, respectively, a bis(phospholy1) triple-decker, (PC4Me4),Co2(Et2C2B3H3) (29), and a phospholyl-pyrrolyl triple-decker, (PC4Me4)Co(Et&,B3H3)Co(NC4Me4) (30). All of the new double-and triple-decker sandwich species were isolated via column and/or plate chromatography as crystalline solids or oils and were characterized via multinuclear NMR, IR, UV-visible, and mass spectra, supported by X-ray diffraction data on 9 (to be reported elsewhere) and 30. Except for 22,23,27, and 28, all new complexes are air-stable. Cyclic voltammetry on 5a/5b, 8a/8b, 9, and 27-30 in dichloromethane...

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Ein neuer Weg zu Tetracarba‐nido‐octaboranen(8); Struktur eines 6,9‐Diferra‐5,7,8,10‐tetracarba‐nido‐decaboran(10)‐Derivats

1997

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ZUSCHRIFTEN miert werden. Nach jeder Steigerung des Oberflachendrucks wurde dem System Zeit zur Gleichgewichtseinstellung gegeben. Gewohnlich wurden Schritte von 2 mNm-' gewahlt. Die Subphase war Wasser (Millipore, Q-Qualitat) rnit einem Widerstand von mehr als 18 Mncm. Die Eintauchgeschwindigkeit wurde auf 0.5 cmmin-' eingestellt. Die Filme wurden fur die Messungen des linearen Dichroismus im Infraroten auf optisch poliertes Calciumtluorid (notigenfalls rnit drei Schichten Behensaure beschichtet) oder Zinkselenid sowie auf optisch poliertes Glas (notigenfalls mit Dichlordimethylsilan vorbehandelt) fur Rontgen-Kleinwinkelstreuexperimente transferiert.IR-Spektren wurden auf einem FT-IR-750-Nicolet-Spektrometer aufgenommen. Die Messung des linearen Dichroismus im Infraroten wurde durchgefuhrt, um das gewohnliche dichroitische Verhaltnis [ R = A(i = 60")/A(i = 0' ) mit A(i) = Absorptionskoeftizient, i = Winkel zwischen der Ebene des LB-Films und dem elektrischen Vektor des IR-Lichts] zu berechnen. Das Verhaltnis R hangt mit dem Grad der Anisotropie aul3erhalb der Tragerebene zusammen und ermoglicht die Berechnung des Winkels q5 zwischen der Senkrechten auf den Trager und dem Dipolmoment einer speziellen Schwingung [21] rnit einer Prazision von wenigen Grad. Rontgenbeugungsexperimente (8-28-Scans) wurden mit einem INEL-Kurvendetektor durchgefiihrt, der zur Reflexzuordnung an einen IBM-Computer angeschlossen war [22]. Die magnetische Suszeptibilitat wurde mit einem SQUID-Magnetometer (Quantum Design MPMS-5) zwischen 2 und 300 K bestimmt. Dafur wurden ca. 300 Schichten auf einer diamagnetischen Mylar-Schicht (0.075 x 5 x 15 mm') aufgebracht. In zwei aufeinanderfolgenden Experimenten wurden unter denselben experimentellen Bedingungen (angelegtes Magnetfeld 1 T) nur der TrPger und danach der Trager rnit dem LB-Film gemessen. Die Differenz liefert die intrinsiscbe magnetische Suszeptibilitat des LB-Films. Der experimentelle Fehler der berechneten Suszeptibilitat der Multischicht konnte auf ca. 5% oberhalb 10 K, ca. 15% bei 100 K und uber 30% bei 300 K geschatzt werden. Eingegangen am 4. November 1996 [Z 97201Stichworte: Dunne Filme -Komposite -Magnetische Eigenschaften ' Monoschichten Polyoxometallate

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Seven-vertex phosphinohalometallacarboranes of iron, cobalt, and nickel: syntheses, structures, and reactions

Cited by 39 publications

References 2 publications

Formation of B−P Bonds through the Reaction of nido-Monophosphinocarboranes with Palladium(II) Complexes. The First Example of a Chelating R₂P−C−B−PR₂ Diphosphine

Formation of B−P Bonds through the Reaction of nido-Monophosphinocarboranes with Palladium(II) Complexes. The First Example of a Chelating R₂P−C−B−PR₂ Diphosphine

Organotransition-metal metallacarboranes. 21. Transition-metal sandwich complexes of heterocyclic ligands. Carborane-stabilized .eta.5-pyrrolyl and .eta.5-phospholyl double-decker and triple-decker compounds: synthesis, structure, and electrochemistry

Ein neuer Weg zu Tetracarba‐nido‐octaboranen(8); Struktur eines 6,9‐Diferra‐5,7,8,10‐tetracarba‐nido‐decaboran(10)‐Derivats

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Seven-vertex phosphinohalometallacarboranes of iron, cobalt, and nickel: syntheses, structures, and reactions

Cited by 39 publications

References 2 publications

Formation of B−P Bonds through the Reaction of nido-Monophosphinocarboranes with Palladium(II) Complexes. The First Example of a Chelating R2P−C−B−PR2 Diphosphine

Formation of B−P Bonds through the Reaction of nido-Monophosphinocarboranes with Palladium(II) Complexes. The First Example of a Chelating R2P−C−B−PR2 Diphosphine

Organotransition-metal metallacarboranes. 21. Transition-metal sandwich complexes of heterocyclic ligands. Carborane-stabilized .eta.5-pyrrolyl and .eta.5-phospholyl double-decker and triple-decker compounds: synthesis, structure, and electrochemistry

Ein neuer Weg zu Tetracarba‐nido‐octaboranen(8); Struktur eines 6,9‐Diferra‐5,7,8,10‐tetracarba‐nido‐decaboran(10)‐Derivats

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Formation of B−P Bonds through the Reaction of nido-Monophosphinocarboranes with Palladium(II) Complexes. The First Example of a Chelating R₂P−C−B−PR₂ Diphosphine

Formation of B−P Bonds through the Reaction of nido-Monophosphinocarboranes with Palladium(II) Complexes. The First Example of a Chelating R₂P−C−B−PR₂ Diphosphine