Naphtho[1,8‐b,c]phosphete and 1,2‐Diphosphaacenaphthene from the Reaction of 1,8‐Dilithionaphthalene with RPCl2

Mizuta, Tsutomu; Nakazono, Tooru; Miyoshi, Katsuhiko

doi:10.1002/anie.200390196

Cited by 6 publications

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“…For example, the P–P bond energy of Et 2 P–PEt 2 is reported to be 86 kcal/mol . However, it is also well-known that the P–P bonds of diphosphine-bridged binuclear complexes can be readily cleaved to form bisphosphido complexes upon heating. − To increase the thermodynamic stability of the P–P bond of diphosphine, we recently reported a novel diphosphine ligand, 1 , in which two phosphorus atoms are locked with a robust naphthalene group, rendering the bond fairly stable . In fact, naphthalene-1,8-diphenyldiphosphine ( 1 ) works as a more thermally stable bridging ligand for group 6 and 11 metal fragments.…”

Section: Introductionmentioning

confidence: 99%

Formation of a Hexacarbonyl Diiron Complex Having a Naphthalene-1,8-bis(phenylphosphido) Bridge and the Electrochemical Behavior of Its Derivatives

et al. 2013

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The P–P bond of the cis-1 ligand in (μ-cis-1)[Fe(CO)4]2 (cis-1 = naphthalene-1,8-diphenyldiphosphine) was cleaved by the two iron centers after CO dissociation from the iron centers, although the P–P bond of cis-1 was stereochemically stabilized with a robust naphthalene group, unlike the usual diphosphines, which lack such support. The resulting (μ-nabip)[Fe(CO)3]2 (3; nabip = naphthalene-1,8-bis(phenylphosphido)) had the diiron core linked by the bisphosphido bridge. Since the trans isomer (μ-trans-1)[Fe(CO)4]2 was stable under ambient conditions, the cis disposition of the two Fe(CO)4 fragments was responsible for the cleavage of the P–P bond. The one or two terminal CO ligands of 3 can be replaced by MeCN and a range of phosphine ligands: i.e., PMe3, PPh3, cis-1, and trans-1. Interestingly, it was found that the diphosphine cis-1 could coordinate the iron center in an unusual κ2 fashion to form a three-membered ring, which was confirmed by NMR spectra as well as X-ray analysis. These diiron complexes can be protonated with the strong acid TfOH in CH2Cl2 to form cationic complexes having a μ-H bridge between the two iron centers. The parent hexacarbonyl complex 3 could act as a proton reduction catalyst at −2.0 V in the presence of TsOH as the proton source in CH2Cl2. When protonated complexes having MeCN or phosphine ligands were used, the proton reduction potentials catalyzed by these complexes were shifted to a more positive range of around −1.77 to −1.37 V, depending on the terminal ligand.

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Section: Introductionmentioning

confidence: 99%

Formation of a Hexacarbonyl Diiron Complex Having a Naphthalene-1,8-bis(phenylphosphido) Bridge and the Electrochemical Behavior of Its Derivatives

et al. 2013

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“…On the other hand, Pd complexes bearing anionic P(V) ligands have been reported to be active catalysts for a cross-coupling reaction of electronically deactivated aryl chlorides. − Since Li’s first report, interest in these P(V) ligands is rapidly increasing. − In our previous reports on an unusual phosphacycle, it has been demonstrated that a platinum fragment was inserted readily into a strained four-membered phosphacycle of peri-phosphorus-bridged naphthalene to form a five-membered P(III)-phosphaplatinacycle (eq ). − …”

Section: Introductionmentioning

confidence: 99%

Synthesis and Reactivity of Five-Membered P(V)-Phosphapalladacycles

et al. 2009

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Reactions of Pd(PPh 3 ) 4 with P(dE)(N i Pr 2 )(naph) (6, E ) S; 7, E ) O) (naph ) 1,8-naphthylene) having a strained four-membered P(V)-phosphacycle gave dimeric complexes [Pd{κ 2 P,C-µ 2 -PE-P(dE)(N i Pr 2 )(naph)}(PPh 3 )] 2 (9, E ) S; 10, E ) O), in which a Pd metal has been inserted into a P-C bond of the phosphacycle to form a phosphapalladacycle having a P(V) donor, and the two phosphapalladacycle units have been mutually bridged with EdP groups, as confirmed by X-ray structure analysis for thermodynamically more stable racemic isomers 9a and 10a. The meso-to-racemic isomerization observed for the simultaneously formed meso isomer 9b, and probably also for the corresponding meso isomer 10b, indicated partial dissociation of 9 and 10 taking place to their monomer units in solution, which were actually trapped as [Pd{κ 2 P,C-P(dE)(N i Pr 2 )(naph)}(dppe)] by treatment with bidentate dppe (dppe ) 1,2-bis(diphenylphosphino)ethane). On the other hand, a similar treatment of 9a with monodentate PMe 3 and PEt 2 Ph resulted in a trivial substitution of both PPh 3 ligands to give dimeric PMe 3 and PEt 2 Ph analogues of 9a, respectively. 10a was found to react with O 2 to form an unprecedented oxidation product, [Pd{κ 2 P,O-µ 2 -PO-PO(dO)(N i Pr 2 )(naph)}(PPh 3 )] 2 , 17, in which an oxygen atom has been inserted into each P(V)-Pd bond. 9a and 10a exhibited moderate catalytic activities for a Heck reaction between PhI and styrene. The mercury test indicated that metallic Pd nanoparticles released from 9a and 10a would be practical catalysts.

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PhP–PPh group bound to 1,8-positions of naphthalene: Preparation of cis isomer and synthesis of binuclear complex

Teramoto¹,

Kubo²,

Mizuta³

2011

Journal of Organometallic Chemistry

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Naphtho[1,8‐b,c]phosphete and 1,2‐Diphosphaacenaphthene from the Reaction of 1,8‐Dilithionaphthalene with RPCl₂

Cited by 6 publications

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Formation of a Hexacarbonyl Diiron Complex Having a Naphthalene-1,8-bis(phenylphosphido) Bridge and the Electrochemical Behavior of Its Derivatives

Formation of a Hexacarbonyl Diiron Complex Having a Naphthalene-1,8-bis(phenylphosphido) Bridge and the Electrochemical Behavior of Its Derivatives

Synthesis and Reactivity of Five-Membered P(V)-Phosphapalladacycles

PhP–PPh group bound to 1,8-positions of naphthalene: Preparation of cis isomer and synthesis of binuclear complex

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