2008
DOI: 10.1002/ange.200801850
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Diphosphinite AgI and PdII Dinuclear Complexes as Adaptable Anion Receptors: An Unprecedented Bridging Mode for the PF6 Ion

Abstract: The special guest: In the host–guest chemistry of dinuclear complexes that contain the 9H‐fluorene‐9,9′‐dimethanediphenylphosphinite ligand the synergy between the phenyl groups and the axial fluorene moiety leads to the formation of molecular cavities that have selective steric affinity for the anions BF4− or PF6− (see picture). An unprecedented M⋅⋅⋅F(PF5)⋅⋅⋅M bridging coordination mode of PF6− has now been established.

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Cited by 7 publications
(5 citation statements)
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“…99-7.33 (br m, 13 H; H 5 Py, Ph), 7.33-7.47 (br m, 2 H; H 3 Py), 7.60 (br d, 3 JA C H T U N G T R E N N U N G (H,H) = 7.7 Hz, 4 H; H 3 Py), 7.68-7.96 (m, 8 H; H 4 Py, H 6 Py), 8.12-8.42 ppm (br m, 4 H; H 6 Py); 13 C{ 1 H} NMR (75 MHz, CD 2 Cl 2 ): d = 22.1 (s; C=CCH 2 CH 2 ), 22.4 (s; C=CCH 2 CH 2 ), 28.2 (s; C=CCH 2 ), 28.5 (s; C=CCH 2 ), 123.6 (s; C 5 Py), 123.7 (s; C 5 Py), 126.1 (s; C 3 Py), 128.9 (s; C Ph ), 129.5 (br s; C Ph ), 130.5 (br s; C Ph ), 131.9 (s; C Ph ), 132.1 (br s; C Ph ), 133.0 (m; C Ph ), 137. 8-139.2 (br m; C 4 Py, C 6 Py), 139.0 (s; C 4 Py), 150.7 (s; C 6 Py), 154.0 ppm (m; C b Py); C 2 Py, C a and ipso-Ph not observed; 31 P{ 1 H} NMR (121 MHz, CD 2 Cl 2 ): d = 5.1-15.2 (m; P phosphole ); 19 [(1-Phenyl-2,5-bis(2-pyridyl)phosphole) 4 (4,4'-bipyridine) 2 Ag 4 ]A C H T U N G T R E N N U N G (PF 6 ) 4 A C H T U N G T R E N N U N G (7 a): To a CH 2 Cl 2 solution (15 mL) of C (50 mg, 0.14 mmol) one equivalent of AgPF 6 (35 mg, 0.14 mmol) was added. This mixture was stirred for 15 min at room temperature in darkness.…”
Section: Methodsmentioning
confidence: 99%
See 1 more Smart Citation
“…99-7.33 (br m, 13 H; H 5 Py, Ph), 7.33-7.47 (br m, 2 H; H 3 Py), 7.60 (br d, 3 JA C H T U N G T R E N N U N G (H,H) = 7.7 Hz, 4 H; H 3 Py), 7.68-7.96 (m, 8 H; H 4 Py, H 6 Py), 8.12-8.42 ppm (br m, 4 H; H 6 Py); 13 C{ 1 H} NMR (75 MHz, CD 2 Cl 2 ): d = 22.1 (s; C=CCH 2 CH 2 ), 22.4 (s; C=CCH 2 CH 2 ), 28.2 (s; C=CCH 2 ), 28.5 (s; C=CCH 2 ), 123.6 (s; C 5 Py), 123.7 (s; C 5 Py), 126.1 (s; C 3 Py), 128.9 (s; C Ph ), 129.5 (br s; C Ph ), 130.5 (br s; C Ph ), 131.9 (s; C Ph ), 132.1 (br s; C Ph ), 133.0 (m; C Ph ), 137. 8-139.2 (br m; C 4 Py, C 6 Py), 139.0 (s; C 4 Py), 150.7 (s; C 6 Py), 154.0 ppm (m; C b Py); C 2 Py, C a and ipso-Ph not observed; 31 P{ 1 H} NMR (121 MHz, CD 2 Cl 2 ): d = 5.1-15.2 (m; P phosphole ); 19 [(1-Phenyl-2,5-bis(2-pyridyl)phosphole) 4 (4,4'-bipyridine) 2 Ag 4 ]A C H T U N G T R E N N U N G (PF 6 ) 4 A C H T U N G T R E N N U N G (7 a): To a CH 2 Cl 2 solution (15 mL) of C (50 mg, 0.14 mmol) one equivalent of AgPF 6 (35 mg, 0.14 mmol) was added. This mixture was stirred for 15 min at room temperature in darkness.…”
Section: Methodsmentioning
confidence: 99%
“…It is noteworthy that similar host-guest interactions between weakly coordinating anions (PF 6 À , BF 4 À ) and cationic Pd II -dimer cavities have recently been reported. [19] In these complexes, modifying the size of the anion results in major conformational changes of dipalladium complexes.…”
Section: Wwwchemeurjorgmentioning
confidence: 99%
“…Despite the fact that PF 6 À is known as a weakly coordinating counterion, such coordination modes due to weak metal-fluorine interactions have been reported previously. [18,19] These results show that treating 1' with metal-based linkers exhibiting no, or at least very weak, attractive metallophilic interactions, the competitive formation of two derivatives, either a metallocyclophane or a coordination polymer, is possible.…”
Section: Notably Each Hgmentioning
confidence: 96%
“…His research focuses on polytopic phosphorus ligands, heterometallic complexes with silicon‐containing ligands, and molecular clusters. He recently reported in Angewandte Chemie on dinuclear silver(I) and palladium(II) diphosphonite complexes that can selectively trap BF 4 − or PF 6 − ions,3b and in the European Journal of Inorganic Chemistry on mono(aryloxido)titanium(IV) complexes and their use in the dimerization of ethene 3c …”
Section: Awarded…︁mentioning
confidence: 99%