Stereochemical control of the redox potential of tetracoordinate rhodium complexes

Angewandte Chemie - International Edition

Volumn 43, Issue 19, 2004, Pages 2567-2570

  Laporte, Cécile ^a   Breher, Frank ^a   Geier, Jens ^a   Harmer, Jeffrey ^a   Schweiger, Arthur ^a   Grützmacher, Hansjörg ^a  

^a ETH ZURICH   (Switzerland)

Author keywords

Electrochemistry; Phosphane ligands; Redox chemistry; Rhodium; Stereochemistry

Indexed keywords

CHELATION; COMPLEXATION; ISOMERS; ORGANOMETALLICS; PROPANE; REDOX REACTIONS; REDUCTION; STEREOCHEMISTRY;

LIGAND TRANSFER; REDOX POTENTIALS; TETRACHELATION; TETRACOORDINATION;

RHODIUM;

1,3 BIS(5H DIBENZO[A,D]CYCLOHEPTEN 5 YL)PHENYLPHOSPHANYLPROPANE; ALKANE DERIVATIVE; RHODIUM COMPLEX; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL ANALYSIS; CHEMICAL REACTION KINETICS; CHEMICAL STRUCTURE; COMPLEX FORMATION; DIASTEREOISOMER; ISOMER; OXIDATION REDUCTION REACTION; STEREOCHEMISTRY;

EID: 4644265479     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200353027     Document Type: Article

References (17)

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12. 2), CCDC-229383 (meso-6), CCDC-229385 rac-7·2THF contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam. ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB21EZ, UK; fax: (+44)1223-336-033; or deposit@ccdc.cam.ac.uk).
13. Alternatively, the distortion can be described by the deviation of Ct from the plane running through the P-Rh-P plane: meso-6: 25.1 pm (Ct1), -66.3pm (Ct2); rac-6: 81.5 and 78.7pm (Ct1), -95.4 and -68.2 pm; rac-7: 100.2 pm (Ct1), -115.3 pm (Ct2).
14. 2 = -1.53 V; S. Deblon, Dissertation, ETH Zürich, 2000, No. 13920.
15. The EPR parameters were obtained by calculating the experimental spectra (least-squares-fittings using EasySpin, see: http ://www.esr.ethz.ch).
16. 0[3] where the Rh-P bond lengths show a linear inverse correlation with the hyperfine couplings.
17. Experiments with the corresponding diastereomers of [M]bis-(tropp)}] with M = Ir or Pt show the same behavior as reported here for M = Rh; C. Laporte, Dissertation, ETH Zürich, 2003, No. 15137.