HYBRID PHOSPHINE-CROWN ETHER LIGANDS: THE STUDY OF BENZO-15-CROWN-5 AND N-PHENYLAZA-15-CROWN-5 AND -18-CROWN-6 FUNCTIONALIZED WITH Ph<sub>2</sub>P-

Muehl, Brian S.; Sheu, Bing-Jahn; Burns, Scot A.; Fritz, James E.; Tribbett, David A.; Weitgenant, Jeremy A.; Storhoff, Bruce N.; Huffman, John C.

doi:10.1080/00958979508024048

Cited by 10 publications

(6 citation statements)

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“…Since the first report by Shaw et al in 1978, [4] several examples of hybrid crown ether phosphane ligands have appeared in the literature. [5][6][7][8][9][10][11] Okano and coworkers have reported the synthesis of mono [3,4-(crown)phenyl]diphenylphosphane ligands PAr*Ph 2 with crown heterocycles of different sizes. [6] The water solubility of these phosphanes is low but the crown cavity acts as an extractant and phase-transfer agent for biphasic catalysis.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Palladium(II) and Platinum(II) Complexes with Crown Ether Phosphane Ligands: Stille Coupling of Aryl Iodides in Water

et al. 2005

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The crown ether phosphanes PAr*Ph2 (1) and PAr*2R [Ar* = 3,4‐(18‐crown‐6)‐phenyl; R = Me (2); R = Ph (3)], prepared from PCl2R and Ar*Li, have been studied. The syntheses and characterization of their oxides (4–6), and their BH3 (7–9), PdCl2 (10–12), and PtCl2 (13–15) complexes are reported. The molecular structure of the borane complex PAr*2Ph·BH3 (9) has been determined by X‐ray structural analysis. Spectroscopic data suggest that phosphanes 1–3 have similar electronic properties and steric requirements to the corresponding phenylphosphane ligands PPh2Me and PPh3. Crown ether methylphosphane 2 and its complexes are remarkably water soluble, but 1 and 3 are only slightly soluble. Palladium(II) complexes 14 and 15 have been tested as catalysts in the Stille coupling of phenyltrichlorostannanes and aryl iodides in water. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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Section: Introductionmentioning

confidence: 99%

Synthesis of Palladium(II) and Platinum(II) Complexes with Crown Ether Phosphane Ligands: Stille Coupling of Aryl Iodides in Water

et al. 2005

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“…We recently initiated a systematic study of triphenylphosphine-based ligands that have crown ether groups appended to the phenyl rings. Specifically, we have reported the synthesis of 1 , the υ(CO) stretching frequencies of the Ni(CO) 3 L complexes of 1 and 2 , and the molecular structure of the oxide of 1 …”

Section: Introductionmentioning

confidence: 99%

Phosphines Functionalized with Crown Ether Groups: Synthesis and Study of Systems Incorporating 1,3-Xylyl-18-Crown-5 Units

et al. 1998

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Hybrid phosphine crown ether molecules are obtained from Ph2PCl, PhP(OMe)2, or P(OPh)3 and the carbanions generated by a lithium/bromine exchange reaction between n-butyllithium and 5-bromo-1,3-xylyl-18-crown-5 or 5-bromo-2-methoxy-1,3-xylyl-18-crown-5. With these phosphine systems represented as Ph x P(crown)3 - x , the x = 0−2 and 1−2 members are reported for the former and latter crown ethers, respectively. The A1 υ(CO) stretching frequencies from the Ni(CO)3L (L = Ph x P(crown)3 - x ) complexes are within 0.4 cm-1 of 2068.9 cm-1, the frequency for Ni(CO)3PPh3. For both series of ligands, H or OMe in the 2-position, the υ(CO) stretching frequencies are found to decrease with increasing substitution by the crown ether groups (deceasing x). The addition of Na+−Cs+ (SCN- salts) to the Ni complexes causes the A1 bands to shift to higher frequencies and to broaden. The largest shifts are observed with phosphines substituted with larger numbers of crown ether groups and added Na+ ions. 31P NMR spectral data for the L2PdCl2 complexes of these phosphines are reported. For all ligands, the signals from the trans complexes are observed between 22 and 25 ppm, a range considered consistent with cone angles of ca. 145°. The molecular structure, from X- ray crystallographic studies, of the oxide of the phosphine with x = 2 and H in the 2-position is reported. The crown ether ring is based on regular gauche and anti arrangements of the carbon−carbon and carbon−oxygen bonds, and the planes defined by the benzene ring and the five oxygen atoms form an angle of 38.4°.

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“…It could be that the largest shifts upon the addition of ions are possible with systems containing the substituents like those found in 1 , because added ions have the potential to substantially reduce the conjugation of the nitrogen lone pair with the phenyl ring. Our previous report that the addition of HCl in ether to the complex of 1a caused a shift to 2071.5 cm -1 provides additional support for this latter conclusion …”

Section: Resultsmentioning

confidence: 58%

“…A wide variety of experimental methods have been used to quantify the donor/acceptor properties of phosphines, including calorimetry, , nonaqueous titrations, , and electrochemical methods − along with NMR and IR 19-21 studies of Ni(CO) 3 L complexes. The latter method was selected for this study so that the data could be directly compared to previous reports from related molecules including 1b . , …”

Section: Resultsmentioning

confidence: 99%

“…We have been interested in synthesizing and characterizing new types of phosphines of the types shown in 1 − 3 . , For the systems studied to date, the donor abilities of the P(III) centers, assessed by ν(CO) frequencies of the Ni(CO) 3 L complexes, decreased in the order 2066.3 ( 1a ) > 2068.3 ( 2 11 ) > 2068.5 ( 3c ) > 2068.7 ( 3e ) > 2068.8 ( 3b ) > 2068.9 ( 3d ) > 2069.1 cm -1 ( 3a ) (Table ). That 1a is a significantly better donor than any of the other ligands is apparently the result of two major factors: first, the nitrogen atom in the oxide of 1a has been shown to be planar, indicating that, as expected, the lone pair is conjugated with the benzene ring, and second, the methoxy groups in 3d , e are likely hindered from adopting a conformation where a significant degree of conjugation can take place. The latter conclusion stems from our recently reported X-ray structure of the model compound 4 , which shows the OCH 3 groups to be perpendicular to the phenyl ring faces rather than in the same plane, as reported for unhindered anisoles, , including P(4-C 6 H 4 OCH 3 ) 3 . ,

…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and Study of Triphenylphosphines Functionalized at the 4-Positions through the Nitrogen Atoms in 1,4,7,10-Tetraoxa-13-azacyclopentadecane and the X-ray Structure of the Oxide of the Molecule Substituted at All Three Positions

et al. 2001

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Hybrid phosphine crown ether ligands have been obtained from PhP(OMe) 2 and P(OPh) 3 and carbanions generated by low-temperature Li/Br exchange reactions involving 4′-bromo-N-phenylaza-15-crown-5 and n-butyllithium. The A 1 ν(CO) values for the Ni(CO) 3 L complexes of these phosphines have been found to be 2063.7 and 2060.8 cm -1 , for the bis (1b) and tris (1c) crown species, respectively, indicating the significant electron-donating abilities of the nitrogen atoms. Addition of NaSCN salts in dichloromethane causes these frequencies to increase by 2.40 (1b) and 3.70 cm -1 (1c), indicating that the P(III) centers detect the presence of crown-coordinated ions. The oxide of 1c has been prepared and the X-ray structure obtained. A prominent feature of that structure, R3 h symmetry, is that the nitrogen atoms are nearly planar and the ring carbon-to-nitrogen distances are 1.375 Å, features that are also consistent with a significant amount of sp 2 C-N double-bond character. The phenyl rings are arranged in a typical propeller shape with torsion angles of 132.4°.

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HYBRID PHOSPHINE-CROWN ETHER LIGANDS: THE STUDY OF BENZO-15-CROWN-5 AND N-PHENYLAZA-15-CROWN-5 AND -18-CROWN-6 FUNCTIONALIZED WITH Ph₂P-

Cited by 10 publications

References 10 publications

Synthesis of Palladium(II) and Platinum(II) Complexes with Crown Ether Phosphane Ligands: Stille Coupling of Aryl Iodides in Water

Synthesis of Palladium(II) and Platinum(II) Complexes with Crown Ether Phosphane Ligands: Stille Coupling of Aryl Iodides in Water

Phosphines Functionalized with Crown Ether Groups: Synthesis and Study of Systems Incorporating 1,3-Xylyl-18-Crown-5 Units

Synthesis and Study of Triphenylphosphines Functionalized at the 4-Positions through the Nitrogen Atoms in 1,4,7,10-Tetraoxa-13-azacyclopentadecane and the X-ray Structure of the Oxide of the Molecule Substituted at All Three Positions

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HYBRID PHOSPHINE-CROWN ETHER LIGANDS: THE STUDY OF BENZO-15-CROWN-5 AND N-PHENYLAZA-15-CROWN-5 AND -18-CROWN-6 FUNCTIONALIZED WITH Ph2P-

Cited by 10 publications

References 10 publications

Synthesis of Palladium(II) and Platinum(II) Complexes with Crown Ether Phosphane Ligands: Stille Coupling of Aryl Iodides in Water

Synthesis of Palladium(II) and Platinum(II) Complexes with Crown Ether Phosphane Ligands: Stille Coupling of Aryl Iodides in Water

Phosphines Functionalized with Crown Ether Groups: Synthesis and Study of Systems Incorporating 1,3-Xylyl-18-Crown-5 Units

Synthesis and Study of Triphenylphosphines Functionalized at the 4-Positions through the Nitrogen Atoms in 1,4,7,10-Tetraoxa-13-azacyclopentadecane and the X-ray Structure of the Oxide of the Molecule Substituted at All Three Positions

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HYBRID PHOSPHINE-CROWN ETHER LIGANDS: THE STUDY OF BENZO-15-CROWN-5 AND N-PHENYLAZA-15-CROWN-5 AND -18-CROWN-6 FUNCTIONALIZED WITH Ph₂P-