The geometrical influence of solid-state ion-pair interactions of alkali metal ions with a binuclear iron acyl monoanion, [Fe2(CO)5(C(O)R)(.mu.2-PPh2)2]-(where R = Ph, Me). Structural analyses of the [Li(THF)3]+, [Na(THF)2]+, and [(Ph3P)2N]+ salts

Ginsburg, Robert E.; Berg, Jeremy M; Rothrock, Richard K.; Collman, James P.; Dahl, Lawrence F.

doi:10.1021/ja00518a016

Cited by 20 publications

(1 citation statement)

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“…In these cases, phosphorus atom is connected only to one metal center and can exhibit either pyramidal geometry with one lone pair or planar geometry with the lone pair participating in π bonding , . It should be noted that, among the high number of bridged phosphido complexes,, there are many reports of transition metal complexes featuring non‐bridging, terminal phosphido ligands,, including some supported by nacnac ligands . However, only a handful of known terminal phosphido complexes, incorporate iron and, in most cases, these complexes are supported by carbonyl or cyclopentadienyl co‐ligands.…”

Section: Introductionmentioning

confidence: 99%

Syntheses, Structures and Reactivity of Terminal Phosphido Complexes of Iron(II) Supported by a β‐Diketiminato Ligand

et al. 2018

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We report the synthesis of the first series of terminal phosphido iron complexes supported by a -diketiminato ligand (Dippnacnac) and their catalytic activity in dehydrocoupling of secondary phosphines. Anionic and neutral mono-or diphosphido complexes were obtained from the reaction of [(Dippnacnac)FeCl 2 Li(dme) 2 ] with the R 2 PLi (R = iPr, tBu, Cy, Ph) phosphides by tuning the stoichiometric ratio, polarity of the solvent, and the bulkiness of the substituents at the P-atom. The structures of the synthesized compounds were determined by single-crystal X-ray diffraction, which revealed that the iron [a] Reports by Webster et al. [14,27,43,[98][99][100][101][102] on the use of an iron(II) -diketiminato pre-catalyst, [(Dippnacnac)Fe(CH 2 TMS)] for the hydrophosphination of unsaturated hydrocarbons and dehydrocoupling of primary and secondary phosphines postulated the formation of an intermediate terminal phosphido complex. In the case of hydrophosphination, the authors proposed that the active catalyst is a monomeric phosphido complex; however, the active species was isolated as a bridging complex, [(Dippnacnac)Fe(PRH(CH 2 ) 3 CH=CH 2 )] 2 . [27] Worth emphasizing is that this compound is not only the first -diketiminate iron complex bridged by phosphido groups, but also a perfect example highlighting the catalytic potential of lowcoordinate iron compounds. The hydrophosphination and dehydrocoupling processes are both ideally suited for the synthesis of novel P-containing compounds and their catalytic improvements will expand the access to functionalized phosphines, diphosphanes, and other P-containing derivatives.Recently, we have reported a new synthetic method to access iron(II) phosphanylphosphido complexes using as starting materials the -diketiminato complex [(Dippnacnac)FeCl 2 -Li(dme) 2 ] [103] and lithium salts of diphosphanes, R 2 P-P(SiMe 3 )Li (R = iPr, tBu). [104] Due to the propensity of the diphosphorus ligand to undergo P-P bond cleavage, these iron(II) phosphanylphosphido complexes have rather limited catalytic potential. Considering this limitation, we directed our attention to iron(II) complexes with phosphido R 2 P ligands. In this paper, we detail the syntheses, structures, and spectroscopic characterization of the first series of terminal phosphido Fe II complexes stabilized by -diketiminates. We also discuss their thermal stability and catalytic activity in promoting the dehydrocoupling of secondary phosphines. Reaction of [(Dippnacnac)FeCl 2 ] with Ph 2 PLi:To the suspension of [(Dippnacnac)FeCl 2 ] (0.272 g, 0.5 mmol) in 2.5 mL of solvent (tolu-Eur.

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Section: Introductionmentioning

confidence: 99%

Syntheses, Structures and Reactivity of Terminal Phosphido Complexes of Iron(II) Supported by a β‐Diketiminato Ligand

et al. 2018

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Ion Pairing Effects on Transition Metal Carbonyl Anions

Darensbourg

1985

Progress in Inorganic Chemistry

136

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Vergleich von Arylphosphit‐substituierten Formyl‐ und Acetyl‐Komplexen des Mangans

et al. 1987

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Formyl-Komplexe mit homoleptischen Carbonylubergangsmetall-Fragmenten erweisen sich generell als sehr instabil'), wahrend entsprechende Acetylkomplexe bestandig sind. Wir fanden, daO Phosphit-Substitution Formyl-Verbindungen erheblich zu stabilisieren vermag, so dal3 diese isoliert werden konnen'). Es war damit die Voraussetzung geschden, das Decarbonylierungsverhalten von FormylVerbindungen naher untersuchen zu konnen und es demjenigen von Acetylkomplexen gegenubenustellen. Dariiber hinaus war beabsichtigt, die strukturellen Eigenschaften beider Komplextypen zu vergleichen. Resultate und DiskussiooDie Darstellung von Bis-oder Tris(phosphit)-substituierten Formylmangan-Komplexen 2 erfolgt gemal3 G1. (1) iiber eine Hydridaddition an entsprechend substituierte kationische Carbonyl-Verbindungen ').Anstelle von Natriumtetrahydridoborat in Methanol kann auch Kalium-hydrotriisopropoxyborat 'a.2b) in THF eingesetzt werden. Die Struktur der blangelben kristallinen Verbindung 2c wurde durch eine Rontgenstrukturanalyse gesichert. Auch die spektroskopischen Daten von 2 stehen mit dem vorgeschlagenen Aufbau i m Einklang.In den IR-Spektren von 2a und 2b beobachtet man im

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The geometrical influence of solid-state ion-pair interactions of alkali metal ions with a binuclear iron acyl monoanion, [Fe2(CO)5(C(O)R)(.mu.2-PPh2)2]-(where R = Ph, Me). Structural analyses of the [Li(THF)3]+, [Na(THF)2]+, and [(Ph3P)2N]+ salts

Cited by 20 publications

References 3 publications

Syntheses, Structures and Reactivity of Terminal Phosphido Complexes of Iron(II) Supported by a β‐Diketiminato Ligand

Syntheses, Structures and Reactivity of Terminal Phosphido Complexes of Iron(II) Supported by a β‐Diketiminato Ligand

Ion Pairing Effects on Transition Metal Carbonyl Anions

Vergleich von Arylphosphit‐substituierten Formyl‐ und Acetyl‐Komplexen des Mangans

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