Olefin-Cycloaddition des elektrophilen Phosphinidenkomplexes [iPr2N−P=Fe(CO)4]

Wit, Jan B. M.; Eijkel, Gerno T. van; Kanter, F. J. J. De; Schakel, Marius; Ehlers, Andreas W.; Lutz, Martin; Spek, Anthony L.; Lammertsma, Koop

doi:10.1002/(sici)1521-3757(19990903)111:17<2716::aid-ange2716>3.0.co;2-z

Cited by 15 publications

(1 citation statement)

References 28 publications

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“…Their singlet-type chemistry has been the subject of various reviews, 26,27 to which the interested reader is referred. The pioneering work was done by Mathey, 22,28,29 but also, studies by Lammertsma 30 and our investigations 24,31 contributed to a better understanding of these transient complexes. The product spectrum of these fleeting complexes has been increased continuously to this day.…”

Section: ■ Introductionmentioning

confidence: 66%

M/X Phosphinidenoid Metal Complex Chemistry

et al. 2021

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Conspectus Like singlet carbenes and silylenes, transient electrophilic terminal phosphinidene complexes enabled highly selective synthetic transformations, but the required multistep synthetic protocols precluded widespread use of these P1 building blocks. By contrast, nucleophilic M/Cl phosphinidenoid complexes can be easily accessed in one step from [M(CO) n (RPCl2)] complexes. This advantage and the mild reaction conditions opened broad synthetic applicability that enabled access to a variety of novel compounds. The chemistry will be described in this Account, including bonding and mechanistic considerations derived from high-level density functional theory calculations. In 2007, we gained the first strong evidence for the formation of these thermally labile complexes using two different synthetic approaches: P–H deprotonation and Cl/Li exchange; the latter has become the preferred method. Intense studies revealed that steric demand of the P substituents in combination with metal complexation, a donor solvent, and/or the presence of a crown ether are necessary prerequisites for the formation and especially the usability of these intermediates as novel P1 building blocks. Solution-phase NMR spectroscopy and solid-state X-ray diffraction studies revealed the bonding situation, i.e., a solvent-separated ion pair structure, and typical 31P NMR signatures of the anions. To date, we have established the following reactivity patterns for Li/Cl phosphinidenoid complexes: self-condensations (I), electrophilic and nucleophilic reactions (II), 1,1-additions (III), [2 + 1] cycloadditions (IV), ring expansions (V), and redox reactions (VI). For example, self-condensations can yield dinuclear acyclic or polycyclic diphosphane or diphosphene complexes. Their use as nucleophiles and electrophiles can be employed to access functional phosphane ligands with mixed substitution patterns. 1,1-Addition reactions were a puzzling discovery because the resulting products resembled classical P–C π-bond structures but the bonding was more of a donor-to-phosphorus adduct with significant differences in bonding parameters. Into the same category and also surprising fall formal E–H insertion reactions leading to 1,1′-bifunctional phosphane complexes. To date, the most important synthetic impact was achieved in the chemistry of strained P-heterocyclic ligands such as oxaphosphiranes and azaphosphiridines, obtained via [2 + 1] cycloadditions of the title compounds with carbonyls and imines, respectively. Ring expansions have been shown to yield 1,2-oxaphosphetanes and 1,2-thiaphosphetanes, and because of the pool of industrially important epoxides, this provides straightforward and affordable access to these novel P-heterocyclic ligands, which also promise to be of interest in catalytic applications. Recent developments describe redox transformations of Li/Cl phosphinidenoid complexes into new reactive intermediates such as complexes with open-shell P-functional phosphanyl ligands via oxidative single electron transfer reactions or into te...

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Section: ■ Introductionmentioning

confidence: 66%

M/X Phosphinidenoid Metal Complex Chemistry

et al. 2021

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Highly Strained Organophosphorus Compounds

Slootweg¹

2012

Phosphorus(III) Ligands in Homogeneous Catalysis: Design and Synthesis

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Phosphinidene Addition to Conjugated Allenes

et al. 2009

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Generating the transient electrophilic tungsten pentacarbonyl-phenylphosphinidene complex PhP=W(CO) 5 in the presence of 2,7-dimethylocta-2,3,5,6-tetraene leads to the formation of a 3,4-di-A C H T U N G T R E N N U N G substituted phosphole or a complexed phospholene, depending on the reaction conditions. The formation of the phospholene results from the reaction of PhP=W(CO) 5 with the diallene, while the formation of the phosphole arises from reaction with 3,4-diisopropylidene-cyclobutene, which is formed in situ from the isomerization of the conjugated allene.

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Olefin-Cycloaddition des elektrophilen Phosphinidenkomplexes [iPr2N−P=Fe(CO)4]

Cited by 15 publications

References 28 publications

M/X Phosphinidenoid Metal Complex Chemistry

M/X Phosphinidenoid Metal Complex Chemistry

Highly Strained Organophosphorus Compounds

Phosphinidene Addition to Conjugated Allenes

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