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Diversity in Complexation of [Rh I (cod)] + and [Ir I (cod)] + by Pyridine‐Amine‐Pyrrole Ligands
Author(s) -
de Bruin Bas,
Kicken Reinout J. N. A. M.,
Suos Nicolaas F. A.,
Donners Maurice P. J.,
den Reijer Carolien J.,
Sandee Albertus J.,
de Gelder René,
Smits Jan M. M.,
Gal Anton W.,
Spek Anton L.
Publication year - 1999
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199909)1999:9<1581::aid-ejic1581>3.0.co;2-1
Subject(s) - chemistry , pyridine , amine gas treating , deprotonation , ligand (biochemistry) , medicinal chemistry , hydrogen bond , stereochemistry , pyrrole , nitrogen , molecule , organic chemistry , ion , biochemistry , receptor
Complexation of [Rh I (cod)] + and [Ir I (cod)] + by the new pyridine‐amine‐pyrrole ligands Py–CH 2 –N(R)–CH 2 –Pyr–H (HL R ; R = H, Bzl, Bu) and the corresponding pyridine‐amine‐pyrrolate ligands [Py–CH 2 –N(R)–CH 2 –Pyr] − (L R − ; R = H, Bzl, Bu, CH 2 Py) has been investigated. The neutral ligands HL R (R = H, Bu, Bzl) give [(HL R )M I (cod)] + (M = Rh, Ir) in which HL R acts as a didentate ligand via the pyridine nitrogen (N Py ) and the amine nitrogen (N R amine ). The crystal structures of [(HL H )M I (cod)]PF 6 (M = Rh: [ 1 ]PF 6 and M = Ir: [ 2 ]PF 6 ) have been determined. Deprotonation of [(HL R )M I (cod)] + (M = Rh, Ir; R = H, Bzl, Bu) results in the neutral complexes [(L R )M I (cod)] (M = Rh, Ir) of the mono‐anionic ligands L R − (R = H, Bzl, Bu). In square‐planar [(L H )M I (cod)] (M = Rh: 3 , M = Ir: 4 ), L H − is didentate via N H amine and the pyrrolate nitrogen (N Pyr ). The X‐ray structures of 3 and 4 reveal that in both cases the uncoordinated N Py accepts a hydrogen bond from N H amine . The X‐ray structures of [(L Bzl )M I (cod)] (M = Rh: 5 , M = Ir: 6 ), show that L Bzl − is didentate via N amine and N Pyr for M = Rh and tridentate for M = Ir. In solution L Bzl − is tridentate for both M = Rh and M = Ir. The neutral complexes [{Py–CH 2 –N(R)–CH 2 –Pyr}M I (cod)] (M = Rh, Ir) cannot be oxidised selectively with H 2 O 2 . This is in marked contrast to the previously observed selective oxidation of the corresponding cationic complexes [{Py–CH 2 –N(R)–CH 2 –Py}Rh I (cod)] + . Rhodium complex 5 is an active catalyst for the stereoregular polymerisation of phenylacetylene, whereas iridium complex 6 is inactive.