Metal-Template-Directed Synthesis of Diphosphorus Compounds through Intramolecular Phosphinidene Additions

Vlaar, Mark J. M.; Assema, S.G.A. van; Kanter, Frans J. J. de; Schakel, Marius; Spek, Anthony L.; Lutz, Martin; Lammertsma, Koop

doi:10.1002/1521-3765(20020104)8:1<58::aid-chem58>3.0.co;2-5

Cited by 18 publications

(4 citation statements)

References 30 publications

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“…Since then, the number of known stable phosphinidene complexes has expanded greatly, with new examples of nucleophilic, electrophilic, , and intermediate phosphinidene complexes being reported. Several new synthetic applications of stable phosphinidene complexes have also been described. , …”

Section: Introductionmentioning

confidence: 99%

Reactivity of Terminal, Electrophilic Phosphinidene Complexes of Molybdenum and Tungsten. Nucleophilic Addition at Phosphorus and P−P Bond Forming Reactions with Phosphines and Diphosphines

et al. 2007

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Reaction of the terminal electrophilic phosphinidene complexes [Cp*M(CO)3{PN(i-Pr)2}][AlCl4] (3, M = Mo; 4, M = W) with PEt3 results in replacement of a metal carbonyl by the phosphine. The reactions occur via initial nucleophilic attack by the phosphine at the phosphinidene phosphorus, followed by carbonyl loss and migration of the phosphine to the metal. Reactions of 3 and 4 with bis(dimethylphosphino)methane (dmpm) lead to [Cp*M(CO)2{P(N(i-Pr)2)P(Me2)CH2P(Me2)-κ2 P 1,P 4}][AlCl4] (9, M = Mo; 10, M = W), in which one end of the diphosphine coordinates to phosphorus and the other end coordinates to the metal. The reactions proceed by initial nucleophilic attack by one end of the diphosphine at phosphorus, followed by carbonyl loss and coordination of the other end of the ligand to the metal. Compound 3 (M = Mo) reacts with bis(dimethylphosphino)ethane (dmpe) to give the analogous product [Cp*Mo(CO)2{P(N(i-Pr)2)P(Me2)CH2CH2P(Me2)-κ2 P 1,P 5}][AlCl4] (12), in which the two ends of the dmpe ligand coordinate to phosphorus and molybdenum, respectively. Reaction of compound 4 (M = W) with dmpe leads to two products, [Cp*W(CO)2{P(N(i-Pr)2)P(Me2)CH2CH2P(Me2)-κ2 P 1,P 5}][AlCl4] (13) and [{Cp*W(CO)2(PN(i-Pr)2)}2(μ-dmpe)][AlCl4]2 (14). Compound 13 is analogous to 12. In compound 14, the two ends of the diphosphine ligand displace carbonyl ligands from two molecules of 4, resulting in a novel bis-phosphinidene structure in which the diphosphine ligand bridges two metal centers, each of which retains a terminal phosphinidene ligand. Loss of an additional carbonyl ligand from 12, followed by migration of one end of the phosphine from phosphorus to the metal, results in re-formation of a terminal phosphinidene ligand, leading to [Cp*Mo(CO)(PN(i-Pr)2)(dmpe-κ2 P)][AlCl4] (17). The structural characterization of the phosphine adducts and carbonyl substitution products of the terminal phosphinidene complexes 3 and 4 has provided valuable insights into metal−phosphinidene bonding in these compounds.

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Section: Introductionmentioning

confidence: 99%

Reactivity of Terminal, Electrophilic Phosphinidene Complexes of Molybdenum and Tungsten. Nucleophilic Addition at Phosphorus and P−P Bond Forming Reactions with Phosphines and Diphosphines

et al. 2007

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“…Such phosphiranes coordinated to a transition metal carbonyl complex carrying an additional phosphine ligand are rare. We are aware of only a phosphirane Fe complex with a bidentate diphosphine ligand and bidentate phosphine Mo complexes in which the second phosphine is linked to the phosphirane ring . Finally, the demetalation from the phosphiranes and phosphirenes will be discussed.…”

Section: Resultsmentioning

confidence: 99%

Decomplexation of Phosphirane and Phosphirene Complexes

et al. 2006

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Novel transient phosphinidene complex Ph−PMo(CO)4PMe3, generated from a 7-phosphanorbornadiene precursor, adds to CC and C⋮C bonds to give Mo(CO)4PMe3-complexed phosphiranes and phosphirenes. The cis-PMe3 ligand weakens the interaction between the molybdenum complex and the three-membered ring. Under mild CO pressure the Mo(CO)4PMe3 transition metal group detaches from the phosphorus center of the ring structure by selective CO substitution. The resulting byproduct Mo(CO)5PMe3 can be reused in the synthesis of the phosphinidene precursor.

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“…The generated phosphinidene adds intramolecularly to a C᎐ ᎐ C bond of the other ligand to give the diphosphorus complex 23. 91 The phosphinidene ligand in [Mo 2 (CO) 4 Cp 2 (µ-PC 6 -H 2 Bu t 3 -2,4,6)] has been shown to behave as a robust supporting group, preserving the nuclearity of the dimetallic unit through protonation, halogenation and decarbonylation reactions. However, the Mo-P bond is chemically active under UV conditions, and intramolecular C-H oxidative addition and intermolecular insertion of alkynes can be induced.…”

Section: Phosphorusmentioning

confidence: 99%

6 Nitrogen, phosphorus, arsenic, antimony and bismuth

Burrows

2003

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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Metal-Template-Directed Synthesis of Diphosphorus Compounds through Intramolecular Phosphinidene Additions

Cited by 18 publications

References 30 publications

Reactivity of Terminal, Electrophilic Phosphinidene Complexes of Molybdenum and Tungsten. Nucleophilic Addition at Phosphorus and P−P Bond Forming Reactions with Phosphines and Diphosphines

Reactivity of Terminal, Electrophilic Phosphinidene Complexes of Molybdenum and Tungsten. Nucleophilic Addition at Phosphorus and P−P Bond Forming Reactions with Phosphines and Diphosphines

Decomplexation of Phosphirane and Phosphirene Complexes

6 Nitrogen, phosphorus, arsenic, antimony and bismuth

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