Regiochemistry of Platinum-Catalyzed Hydrophosphination of a Diene. Formation of the Chiral Diphosphine Et2PCH(CN)CH(CH2CH2CN)PEt2 via Monophosphine Intermediates

Kovacik, Ivan; Scriban, Corina; Glueck, David S.

doi:10.1021/om050769q

Cited by 32 publications

(16 citation statements)

References 16 publications

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“…According to Glueck and co‐workers,21a a plausible reaction pathway could be an outer‐sphere mechanism, that is, nucleophilic attack of the phosphanide to the external olefin followed by transfer of the hydride to the resulting carbanion to give the rhodium(I) complex [RhTp(PMe 3 )(Ph 2 P‐CH(CO 2 Me)CH 2 (CO 2 Me)] ( B ). However, based on the observed hydrophosphination of ethylene (see below), a possible inner‐sphere mechanism cannot be excluded.…”

Section: Methodsmentioning

confidence: 99%

Template‐Controlled Assembly of Ditopic Catechol Phosphines: A Strategy for the Generation of Complexes of Bidentate Phosphines with Different Bite Angles

Chikkali

Gudat

Lissner

et al. 2008

Chemistry A European J

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A rational approach to the synthesis of heterobi- or -trimetallic complexes based upon self-assembly of a flexible ditopic catechol-phosphine ligand with [(cod)PdCl(2)] and simple metal halides such as GaCl(3), BiCl(3), SnCl(4), or ZrCl(4) is described. All products were characterized by spectroscopic and analytical data and single-crystal X-ray diffraction studies. The molecular structures can be described in terms of cis-configured palladium complexes with supramolecular bisphosphine ligands that are formed by the assembly of two phosphine catecholate fragments on a main group/transition metal template. Of particular interest are the distinct decreases in P-Pd-P bite angles and P...P distances between the ligating atoms with increasing covalent radii of the templates. The range of these variations is of a magnitude similar to that of the geometrical changes in known families of complexes containing molecular bidentate ligands. Solution NMR studies give further evidence that in several cases the mu(2)-bridging coordination of two of the catechol oxygen atoms in the template complexes is broken under the influence of donor solvents, thus allowing the supramolecular ligand to be switched between tetradentate -O(2)P(2) and bidentate -P(2) coordination modes.

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Section: Methodsmentioning

confidence: 99%

Template‐Controlled Assembly of Ditopic Catechol Phosphines: A Strategy for the Generation of Complexes of Bidentate Phosphines with Different Bite Angles

Chikkali

Gudat

Lissner

et al. 2008

Chemistry A European J

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“…Glueck as well as Bergman and Toste have broadly capitalized on the nucleophilicity of phosphido ligands in phosphination catalysis. 3,80,[104][105][106][107][108][109][110][111][112][113][114] Coupling reactions, such as those between phosphines and aryl halides, have been known for some time. 115 In recent years, these reactions have been applied to the preparation of poly(P-phenylenephosphine)s, conjugated polymers with phosphorus in the main chain.…”

Section: Scheme 20mentioning

confidence: 99%

Metal-phosphido and -phosphinidene complexes in P–E bond-forming reactions

2009

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Metal complexes bearing terminal phosphido or phosphinidene ligands have become versatile tools in the stoichiometric and catalytic preparation of phosphorus-element bonds. This Perspective describes a selection of recent advances in this field, and certain emphasis has been placed on reactions that vary from what has been previously observed. Some of the general reactivity trends and mechanistic understanding in these metal-mediated reactions that has emerged are also described. Much of what is chronicled herein comes from a flux of reports over the last decade describing unique metal-mediated phosphorus-element bond formation reactions that are likely to stimulate further discoveries.

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“…In this context, special attention should be given to terminal low‐coordinated phosphido complexes with pyramidal or planar geometry . 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 .…”

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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Regiochemistry of Platinum-Catalyzed Hydrophosphination of a Diene. Formation of the Chiral Diphosphine Et₂PCH(CN)CH(CH₂CH₂CN)PEt₂ via Monophosphine Intermediates

Abstract: Pt-catalyzed addition of diethylphosphine to the diene cis,cis-mucononitrile gave the new diphosphine Et2PCH(CN)CH(CH2CH2CN)PEt2 as a 3:2 mixture of diastereomers. Two monophosphine−alkene intermediates in the hydrophosphination were characterized by NMR spectroscopy.

Cited by 32 publications

References 16 publications

Template‐Controlled Assembly of Ditopic Catechol Phosphines: A Strategy for the Generation of Complexes of Bidentate Phosphines with Different Bite Angles

Template‐Controlled Assembly of Ditopic Catechol Phosphines: A Strategy for the Generation of Complexes of Bidentate Phosphines with Different Bite Angles

Metal-phosphido and -phosphinidene complexes in P–E bond-forming reactions

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

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