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

Teramoto, Yuichi; Kubo, Kazuya; Mizuta, Tsutomu

doi:10.1016/j.jorganchem.2011.07.030

Cited by 13 publications

(10 citation statements)

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“…We became further interested to compare the reactivity of 1 and 2 with that of Naph 2 P 2 . Naph 2 P 2 was found to react with AuCl(tht) (tht = tetrahydrothiophene) with formation of the binuclear complex [Naph 2 P 2 ][AuCl] 2 as was observed in the reaction of Naph(PPh) 2 , which gave [Naph(PPh) 2 ][AuCl] 2 . In contrast, the reaction of 1 with Me 2 SAuCl proceeded with reduction of Me 2 SAuCl, oxidative cleavage of the As–As bond and formation of Naph 2 (AsCl) 2 7 (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Structure and Reactivity of 1,8-Bis(naphthalenediyl)dipnictanes

et al. 2019

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Syntheses and solid-state structures of diarsane Naph2As2 (Naph = 1,8-naphthalenediyl, 1) and (Naph)5Sb4Cl2 3 are reported and the σ-donor capacity of Naph2E2 (E = As 1, Sb 2) was studied in reactions with (coe)Cr(CO)5 (coe = Z-cyclooctene), yielding Naph2As2[Cr(CO )5]2 (4) and Naph2E2Cr(CO)5 (E = As 5, Sb 6). In contrast, reactions of 1 and 3 with Me2SAuCl proceed with oxidation and formation of elemental gold as well as Naph2(AsCl)2 ( 7) and [NaphSbCl2]2 8. All complexes were characterized by elemental analyses, heteronuclear ( 1 H, 13 C) NMR and FT-IR spectroscopy as well as single crystal X-ray diffraction. Intermolecular E•••π interactions (E = As, Sb), which were observed in 7 and 8, were quantified by use of density functional theory and local coupled cluster electronic structure theory calculations. These allow to assess the nature and relative importance of covalent and non-covalent interactions and illustrate how dispersion interactions change with the electronic structure of the series of compounds.

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Section: Resultsmentioning

confidence: 99%

Structure and Reactivity of 1,8-Bis(naphthalenediyl)dipnictanes

et al. 2019

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“…Cis -diphosphane disulfides (Chart ) have only been achieved by functionalizing bicyclic diphosphanes . Still, cis bicycles are required for this conversion, yet there is only a relatively limited number of reports of diphosphanes with such a locked cis configuration …”

Section: Introductionmentioning

confidence: 99%

Functionalization Reactions Characteristic of a Robust Bicyclic Diphosphane Framework

et al. 2013

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The 3,4,8,9-tetramethyl-1,6-diphospha-bicyclo-[4.4.0]deca-3,8-diene (P2(C6H10)2) framework containing a P-P bond has allowed for an unprecedented selectivity toward functionalization of a single phosphorus lone pair with reference to acyclic diphosphane molecules. Functionalization at the second phosphorus atom was found to proceed at a significantly slower rate, thus opening the pathway for obtaining mixed functional groups for a pair of P-P bonded λ(5)-phosphorus atoms. Reactivity with the chalcogen-atom donors MesCNO (Mes = 2,4,6-C6H2Me3) and SSbPh3 has allowed for the selective synthesis of the diphosphane chalcogenides OP2(C6H10)2 (87%), O2P2(C6H10)2 (94%), SP2(C6H10)2 (56%), and S2P2(C6H10)2 (87%). Computational studies indicate that the oxygen-atom transfer reactions involve penta-coordinated phosphorus intermediates that have four-membered {PONC} cycles. The P-E bond dissociation enthalpies in EP2(C6H10)2 were measured via calorimetric studies to be 134.7 ± 2.1 kcal/mol for P-O, and 93 ± 3 kcal/mol for P-S, respectively, in good agreement with the computed values. Additional reactivity with breaking of the P-P bond and formation of diphosphinate O3P2(C6H10)2 was only observed to occur upon heating of dimethylsulfoxide solutions of the precursor. Reactivity of diphosphane P2(C6H10)2 with azides allowed the isolation of monoiminophosphoranes (RN)P2(C6H10)2(R = Mes, CPh3, SiMe3), and treatment with additional MesN3 yielded symmetric and unsymmetric diiminodiphosphoranes (RN)(MesN)P2(C6H10)2 (91% for R = Mes). Metalation reactions with the bulky diiminodiphosphorane ligand (MesN)2P2(C6H10)2 (nppn) allowed for the isolation and characterization of (nppn)Mo(η(3)-C3H5)Cl(CO)2 (91%), (nppn)NiCl2 (76%), and [(nppn)Ni(η(3)-2-C3H4Me)][OTf] showing that these ligands provide an attractive preorganized binding pocket for both late and early transition metals.

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“…The photochemical trans-cis isomerization of the cyclic diphosphine has been previously reported. 41 In the present case, however, since Cr(CO) 4 (thf ) 2 also gives the κ 2 coordination product without irradiation of the ligand, the isomerization is considered to take place thermally.…”

Section: Synthesis Ofmentioning

confidence: 81%

Synthesis and coordination chemistry of (PNEt₂)₂-bridged [2]ferrocenophanes

et al. 2016

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The trivalent phosphorus-bridged [2]ferrocenophane complex 2 having NEt groups on the respective phosphorus centers was prepared, and its reactions as a diphosphine ligand were examined for iron and chromium carbonyl complexes. Both the phosphorus centers of 2 coordinated to Fe(CO) fragments to form (μ-2)-[Fe(CO)], while the bulkier Cr(CO) fragment formed only a monochromium complex [Cr(κ-2)(CO)]. Dissociation of CO from [Cr(κ-2)(CO)] changed the coordination mode of 2 from κ to κ to form [Cr(κ-2)(CO)] having a three-membered ring. A similar approach for the monoiron complex [Fe(κ-2)(CO)] did not afford a κ complex but instead an EtNPC(O)PNEt-bridged [3]ferrocenophane complex in which a CO fragment was inserted into the P-P bond of 2 and both the phosphorus centers coordinated to Fe(CO) as a chelate diphosphine. The reaction of this product with an Fe(CO) fragment gave μ-{Fe(CHPNEt)-κP:κP}-[Fe(CO)] (8), in which one terminal CO and the CO group between the two phosphorus atoms were lost to give an [FeFe]hydrogenase mimic having a bis(phosphido)ferrocene chelate as a bridging unit. The two NEt groups of the bridging unit were expected to work as protonation sites. The protonated NEt groups contributed to an improvement in the reduction potential of the complex to a less negative area, i.e., -2.3 V for the free 8 to -1.0 V for the diprotonated 8. The catalytic reduction of the proton, however, required a more negative potential of -2.0 V, which is almost comparable to that of the phosphido-bridged [FeFe]hydrogenase model complex having no protonation site.

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

Cited by 13 publications

References 33 publications

Structure and Reactivity of 1,8-Bis(naphthalenediyl)dipnictanes

Structure and Reactivity of 1,8-Bis(naphthalenediyl)dipnictanes

Functionalization Reactions Characteristic of a Robust Bicyclic Diphosphane Framework

Synthesis and coordination chemistry of (PNEt₂)₂-bridged [2]ferrocenophanes

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

Cited by 13 publications

References 33 publications

Structure and Reactivity of 1,8-Bis(naphthalenediyl)dipnictanes

Structure and Reactivity of 1,8-Bis(naphthalenediyl)dipnictanes

Functionalization Reactions Characteristic of a Robust Bicyclic Diphosphane Framework

Synthesis and coordination chemistry of (PNEt2)2-bridged [2]ferrocenophanes

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Synthesis and coordination chemistry of (PNEt₂)₂-bridged [2]ferrocenophanes