Rhenium carbonyl complexes with monodentate-coordinated diphosphines: activation of terminal phosphino groups towards amine-oxide oxidation

Fan, Wei; Zhang, Rui; Leong, Weng Kee; Chu, Chit Kay; Yan, Yaw Kai

doi:10.1016/j.jorganchem.2005.05.010

Cited by 11 publications

(3 citation statements)

References 15 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…X-ray diffraction of single crystals revealed 3 to be the product of oxidation of the central NHP phosphorus, [P(PO)P]Co(CO) 2 (Figure ), to generate an N-heterocyclic phosphinito complex. While there are many examples of metal-bound phosphorus oxidation by trimethylamine N -oxide, − to our knowledge, this is the first isolated example of an oxidized NHP. The most striking feature of the solid-state structure of 3 is a Co–P NHP distance significantly shorter than that observed in the phosphorus(III) precursor 2 (2.1675(5) Å vs 2.2386(6) Å).…”

mentioning

confidence: 79%

Coordination of an N-Heterocyclic Phosphenium Containing Pincer Ligand to a Co(CO)₂ Fragment Allows Oxidation To Form an Unusual N-Heterocyclic Phosphinito Species

et al. 2011

View full text Add to dashboard Cite

A tridentate pincer ligand featuring a central Nheterocyclic phosphenium (NHP + ) donor has been coordinated to a Co(CO) 2 fragment to generate the Co NHP complex [PPP]Co(CO) 2 (2). The NHP unit adopts an unusual pyramidal geometry with a relatively long Co−P distance, suggesting a stereochemically active nonbonding phosphorus lone pair. Interestingly, treatment of 2 with trimethylamine N-oxide affords [P(PO)P]Co(CO) 2 (3), in which the Co-bound central phosphorus donor has been oxidized to an unprecedented N-heterocyclic phosphinito species. The bonding and electronic properties of these complexes are discussed in the context of DFT and NBO computational data. W hile N-heterocyclic carbene ligands (NHCs) have become ubiquitous in the field of transition metal and organo-catalysis, 1−5 far less focus has been placed on the potential applications of their isovalent group 15 analogues, Nheterocyclic phosphenium cations (NHPs). 6−10 First reported in 1972, 11,12 theoretical investigations of the electronic structure of NHPs have shown that they are poor σ donors but excellent π acceptors, in contrast to NHCs, which are very good σ-donors and poor π-acceptors. Recent advancements in the chemistry of NHPs include new preparative methods 13−16 and new reactivity patterns, 13,17−19 but the coordination chemistry and catalytic capabilities of NHPs are relatively unexplored compared to their NHC counterparts.One of the more interesting aspects of NHP ligands is their ability to adopt different binding modes toward transition metals depending on the electronic nature of the transition metal center. Most commonly, when binding to an electronpoor fragment, NHPs act as both σ-donors and π-acceptors, leading to a planar geometry at the phosphorus atom (NHP + description). However, when binding to an electron-rich fragment, NHPs adopt a pyramidal geometry indicative of a nonbonding phosphorus lone pair. Two limiting descriptions for the bonding in such pyramidal NHPs have been suggested:(1) the Lewis acidic NHP phosphorus acts solely as an electron pair acceptor (NHP + /M n ) and (2) the bonding between the metal and the NHP is covalent and the NHP is best described as a phosphido ligand (NHP − /M n+2 ). In this sense, a convincing analogy between NHPs and nitrosyls, which can adopt either linear or bent geometries, can be made, 17 highlighting the potential noninnocent character of these ligands and bringing about potential ambiguities in the formal metal oxidation state. Key advantages of phosphenium ligands over their noninnocent nitrosyl counterparts are (1) the ability to modify their steric and electronic properties via derivatization and (2) the ability to incorporate these ligands into chelating frameworks. These strategies may also be effective at imparting stability in transition-metal NHP complexes and protecting them from nucleophilic attack. Transition-metal complexes of multidentate ligands featuring NHPs are noticeably absent from the literature, particularly in comparison to the growing number of NHC-containing...

show abstract

mentioning

confidence: 79%

Coordination of an N-Heterocyclic Phosphenium Containing Pincer Ligand to a Co(CO)₂ Fragment Allows Oxidation To Form an Unusual N-Heterocyclic Phosphinito Species

et al. 2011

View full text Add to dashboard Cite

show abstract

“…In the latter case it has been suggested that the oxygen transfer may be metal-assisted. A more recent study suggests that oxidation of the pendant phosphine moiety occurs via an intramolecular pathway involving interaction of the uncoordinated phosphorus atom with a carbonyl ligand to form a cyclic intermediate [25].…”

Section: Minor Productsmentioning

confidence: 99%

Ditertiary phosphine derivatives of the heteronuclear cluster RuOs3(μ-H)2(CO)13

Tan

Leong

2007

Journal of Organometallic Chemistry

Self Cite

View full text Add to dashboard Cite

“…The coordination chemistry of such “phosphomide” ligands is, nonetheless, scant and largely restricted to groups 6–8 (Cr, Mo,, W, Mn, Re, Fe, Ru) with an emphasis on the first‐row metals. A limited range of group 9 complexes has been described with “Cp′RhCl 2 ” (Cp′ = Cp, Cp*) and “Cp*IrCl 2 ” fragments; however, trans ‐Rh(CO)(L) 2 Cl (L = PH 2 {C(O)Me}, PPh 2 {C(O)C 7 F 15 }, PPh 2 {C(O) p ‐An}) and [Rh{κ 2 ‐ P , P ‐C 6 H 3 N{PC(O)PPh 2 } 2 ‐2,6}Cl][13a] are the only low‐valent group 9 complexes known.…”

Section: Introductionmentioning

confidence: 99%

Aroylphosphanes: Base‐Free Synthesis and Their Coordination Chemistry with Platinum‐Group Metals

2016

View full text Add to dashboard Cite

show abstract

Rhenium carbonyl complexes with monodentate-coordinated diphosphines: activation of terminal phosphino groups towards amine-oxide oxidation

Cited by 11 publications

References 15 publications

Coordination of an N-Heterocyclic Phosphenium Containing Pincer Ligand to a Co(CO)₂ Fragment Allows Oxidation To Form an Unusual N-Heterocyclic Phosphinito Species

Coordination of an N-Heterocyclic Phosphenium Containing Pincer Ligand to a Co(CO)₂ Fragment Allows Oxidation To Form an Unusual N-Heterocyclic Phosphinito Species

Ditertiary phosphine derivatives of the heteronuclear cluster RuOs3(μ-H)2(CO)13

Aroylphosphanes: Base‐Free Synthesis and Their Coordination Chemistry with Platinum‐Group Metals

Contact Info

Product

Resources

About

Rhenium carbonyl complexes with monodentate-coordinated diphosphines: activation of terminal phosphino groups towards amine-oxide oxidation

Cited by 11 publications

References 15 publications

Coordination of an N-Heterocyclic Phosphenium Containing Pincer Ligand to a Co(CO)2 Fragment Allows Oxidation To Form an Unusual N-Heterocyclic Phosphinito Species

Coordination of an N-Heterocyclic Phosphenium Containing Pincer Ligand to a Co(CO)2 Fragment Allows Oxidation To Form an Unusual N-Heterocyclic Phosphinito Species

Ditertiary phosphine derivatives of the heteronuclear cluster RuOs3(μ-H)2(CO)13

Aroylphosphanes: Base‐Free Synthesis and Their Coordination Chemistry with Platinum‐Group Metals

Contact Info

Product

Resources

About

Coordination of an N-Heterocyclic Phosphenium Containing Pincer Ligand to a Co(CO)₂ Fragment Allows Oxidation To Form an Unusual N-Heterocyclic Phosphinito Species

Coordination of an N-Heterocyclic Phosphenium Containing Pincer Ligand to a Co(CO)₂ Fragment Allows Oxidation To Form an Unusual N-Heterocyclic Phosphinito Species