Preparation and properties of tetrahedro-tetraphosphorus complexes of rhodium and iridium.  Molecular and electronic structure of [RhCl(.eta.2-P4)(PPh3)2]

Ginsberg, A. P.; Lindsell, W. Edward; McCullough, Kevin J.; Sprinkle, C. R.; Welch, A.

doi:10.1021/ja00263a010

Cited by 83 publications

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“…The product 3·3 CH 2 Cl 2 was isolated as a red precipitate by filtration, washed with n-pentane (3 2 mL) and dried (loss of 1 CH 2 Cl 2 solvent molecule per asymmetric unit) in dynamic vacuum at 40 8C (0.092 g, 81 %). Crystals of 3·3 CH 2 Cl 2 suitable for X-ray diffraction analysis were obtained at room temperature from slow diffusion of pentane vapour into a solution of 3 in CH 2 16 mmol, 2 equiv), dppm (0.031 g, 0.08 mmol, 1 equiv) and 2 (0.040 g, 0.08 mmol, 1 equiv) CH 2 Cl 2 (10 mL) was stirred overnight. Afterwards, the mixture was filtered and n-pentane (90 mL) was added, leading to the precipitation of light orange 4·CH 2 Cl 2 .…”

Section: Methodsmentioning

confidence: 99%

“…[1,2] A challenge in this field lies in the study of the reactivity pattern of these E n (E = P, As, Sb, Bi) ligand complexes.…”

Section: Introductionmentioning

confidence: 99%

“…To achieve the so far unknown coordination types for phosphorus, a bimetallic approach is useful, in which two Lewis acidic metal centres are already pre-organized to impose a mixed end-on/side-on coordination mode to the tetrahedral complex [{CpMo(CO) 2 [10] (Scheme 2) is an attractive precursor because the coordination sphere of the metal centres has labile acetonitrile ligands that can be replaced through ligand-exchange reactions without the collapse of the bime-A C H T U N G T R E N N U N G tallic entities. [9,11] It will be shown that the reaction of the complex 2 with this precursor allows the synthesis of the first coordination compound in which 2 shows the coordination mode IV.…”

Section: Introductionmentioning

confidence: 99%

“…By the addition of n-pentane, the compound could be isolated as an orange precipitate in 67 % yield. Compound 4 is moderately soluble in CH 2 …”

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confidence: 99%

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Simultaneous End‐On/Side‐On Coordination Modes of a Diphosphorus Tetrahedral Complex Imposed by Pre‐organization of Oligometallic Cu^I Acceptors

Welsch

Lescop

Baláȥs

et al. 2011

Chemistry A European J

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The reaction of the [{CpMo(CO)(2)}(2)(μ,η(2):η(2)-P(2))] (Cp=cyclopentadienyl) metallo-ligand 2 with pre-organized Cu(I) bi- and trimetallic precursors afforded new coordination complexes with unprecedented coordination modes for a Mo(2)P(2) complex. Variable-temperature solution and solid-state (31)P NMR spectroscopy measurements were performed and X-ray diffraction studies revealed an η(2):η(1) coordination mode for the Mo(2)P(2) unit of 2 in the Cu(I) bimetallic complexes 3 and 4. DFT calculations were carried out to highlight the bonding situation of this unprecedented coordination mode in the Cu(I) bimetallic compound 3. It is built up from a side-on coordination of the P-P σ bond to one copper ion and from the interaction of the lone pair of one phosphorus atom with the second copper ion. The remaining available lone pair of the second phosphorus atom can be involved as well to interact with an additional metal centre, as evidenced in the Cu(I) trimetallic compound 5 in which an η(2):η(1):η(1) coordination mode of the ligand 2 is observed. Derivative 3 can be used as a molecular clip to obtain discrete π-stacked dimers through a ligand exchange reaction between acetonitrile ligands and cyano-capped π-conjugated systems, indicating the stability of the new η(2):η(1) coordination mode.

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Section: Methodsmentioning

confidence: 99%

“…[1,2] A challenge in this field lies in the study of the reactivity pattern of these E n (E = P, As, Sb, Bi) ligand complexes.…”

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“…By the addition of n-pentane, the compound could be isolated as an orange precipitate in 67 % yield. Compound 4 is moderately soluble in CH 2 …”

mentioning

confidence: 99%

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Simultaneous End‐On/Side‐On Coordination Modes of a Diphosphorus Tetrahedral Complex Imposed by Pre‐organization of Oligometallic Cu^I Acceptors

Welsch

Lescop

Baláȥs

et al. 2011

Chemistry A European J

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“…[26] Überdies haben die Verbindungen [(Cp''Rh) 4 4 -phosphoran ansehen, das in ein "Push-pull"-System gegenüber einem Cp'''CoFragment eingebettet ist. Letztere Verbindungsklasse ist mittlerweile in der Phosphorchemie [27] etabliert und wird z.…”

Section: Methodsunclassified

Zugang zu ausgedehnten Polyphosphor‐Gerüsten

et al. 2010

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Professor Malcolm H. Chisholm zum 65. Geburtstag gewidmet Die Aktivierung von P 4 -Phosphor ist ein aktuelles Teilgebiet der gegenwärtigen Chemie. Unlängst wurden durch Hauptgruppenelementverbindungen große Fortschritte erzielt, da sie in der Lage sind, eine, [1] zwei [2] oder drei P-P-Bindungen [3] zu öffnen und das P 4 -Molekül zu P 2 -oder P 1 -Einheiten abzubauen.[4] Die Aggregation von P 4 durch N-heterocyclische Carbene (NHCs) hat gezeigt, dass die große P 12 -Einheit in A erhalten werden kann.[5] Weiterhin wurden große kationische (P n + , n 89) [6] und anionische Polyphosphorspezies (P n À , n 49) [6,7] in der Gasphase durch Laserablationstechniken erzeugt. Frühere Untersuchungen in organischen Lösungsmit-teln durch die Gruppe von Baudler führten überdies zu einer großen Zahl an organosubstituierten Polyphosphorverbindungen.[ berichten. [9] Einige davon wurden als Verbindungen isoliert und strukturell charakterisiert, [10] so auch das Polyphosphid P 26 4À .[11]Im Unterschied zu dieser Aktivierung von P 4 unter Verwendung von Hauptgruppenelementverbindungen [12] ist die Aktivierung von P 4 durch Übergangsmetalle ein etabliertes Gebiet [13] und von großem Interesse im Hinblick auf Syntheseverfahren für Organophosphorverbindungen, die PCl 3 als Ausgangsstoff vermeiden. Die bisher größte neutrale P nSpezies, [{(Bu 3 P) 2 Ni} 4 P 14 ] (B), wurde durch Kondensation zweier P 7 -Einheiten ausgehend von Li 3 P 7 ·3 DME synthetisiert.[14] Mit P 4 als Ausgangsverbindung sind die größten[17] (C), in dessen Struktur zwei verknüpfte cyclo-P 5 -Einheiten vorliegen. Der bisher größte 31 P-NMR-spektroskopisch charakterisierte P n -Komplex, der ausgehend von P 4 synthetisiert wurde, ist [(Cp'''Co) 3 P 12 ] (D) (Cp''' = h 5 -C 5 H 2 tBu 3 -1,2,4). Er wurde durch die Gruppe von Scherer als Nebenprodukt (3 %) bei der Cothermolyse von [Cp'''Co(CO) 2 ] und P 4 bei 1908 oder in mäßigen Ausbeuten (23 %) durch Photolyse bei Raumtemperatur erhalten (neben 10 % [(Cp'''Co) 3 P 8 ]).[18] Zusätzlich wurde in beiden Reaktionen [(Cp'''Co) 2 (P 2 ) 2 ] gebildet, in der Thermolyse als Haupt-(22 %) und in der Photolyse als Nebenprodukt (4 %).Angesichts des derzeitigen Wissenstands stellt sich die Frage nach gezielten Synthesewegen für größere neutrale P nAggregate, um die Transformation von P 4 zum Hittorfschen Phosphor [19] oder anderen Polyphosphorstrukturen nachzubilden, die stabiler als P 4 sind.[20] Aus diesem Grund erschien die Nutzung eines ungesättigten Komplexfragments von Vorteil, das P 4 -Tetraeder zu größeren Spezies kombinieren kann. Da offensichtlich Cp R Co-Einheiten eine maßgebliche Rolle in der Stabilisierung großer P n -Einheiten spielen, entschieden wir uns für [(Cp'''Co)

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Synthesis and Characterisation oftetrahedro-Tetraphosphorus Complexes of Rhenium – Evidence for the First Bridging Complex of White Phosphorus

Peruzzini¹,

Marvelli

Romerosa

et al. 1999

Eur. J. Inorg. Chem.

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Reaction of white phosphorus with [(triphos)Re(CO)2(OTf)] (1) in dichloromethane affords the new tetraphosphorus complex [(triphos)Re(CO)2(η1‐P4)](OTf) (2) [triphos = MeC(CH2PPh2)3; OTf = OSO2CF3]. Compound 2 reacts with a second equivalent of 1 to give the binuclear complex [{(triphos)Re(CO)2}2(μ,η1,η1‐P4)](OTf)2 (3) in which a tetrahedro‐P4 ligand behaves as tethering unit between two [(triphos)Re(CO)2]+ moieties. Complexes 2 and 3 represent the first soluble metal complexes of the tetraphosphorus molecule where the P4 ligand has not undergone any major modification.

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Preparation and properties of tetrahedro-tetraphosphorus complexes of rhodium and iridium. Molecular and electronic structure of [RhCl(.eta.2-P4)(PPh3)2]

Cited by 83 publications

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Simultaneous End‐On/Side‐On Coordination Modes of a Diphosphorus Tetrahedral Complex Imposed by Pre‐organization of Oligometallic Cu^I Acceptors

Simultaneous End‐On/Side‐On Coordination Modes of a Diphosphorus Tetrahedral Complex Imposed by Pre‐organization of Oligometallic Cu^I Acceptors

Zugang zu ausgedehnten Polyphosphor‐Gerüsten

Synthesis and Characterisation oftetrahedro-Tetraphosphorus Complexes of Rhenium – Evidence for the First Bridging Complex of White Phosphorus

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Preparation and properties of tetrahedro-tetraphosphorus complexes of rhodium and iridium. Molecular and electronic structure of [RhCl(.eta.2-P4)(PPh3)2]

Cited by 83 publications

References 0 publications

Simultaneous End‐On/Side‐On Coordination Modes of a Diphosphorus Tetrahedral Complex Imposed by Pre‐organization of Oligometallic CuI Acceptors

Simultaneous End‐On/Side‐On Coordination Modes of a Diphosphorus Tetrahedral Complex Imposed by Pre‐organization of Oligometallic CuI Acceptors

Zugang zu ausgedehnten Polyphosphor‐Gerüsten

Synthesis and Characterisation oftetrahedro-Tetraphosphorus Complexes of Rhenium – Evidence for the First Bridging Complex of White Phosphorus

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Simultaneous End‐On/Side‐On Coordination Modes of a Diphosphorus Tetrahedral Complex Imposed by Pre‐organization of Oligometallic Cu^I Acceptors

Simultaneous End‐On/Side‐On Coordination Modes of a Diphosphorus Tetrahedral Complex Imposed by Pre‐organization of Oligometallic Cu^I Acceptors