Abstract
The addition of aminoalkyl-substituted 2,6-bis(imino)pyridine (or pyridine diimine, PDI) ligands to [(COD)RhCl]2 (COD = 1,5-cyclooctadiene) resulted in the formation of rhodium monochloride complexes with the general formula (NPDI)RhCl (NPDI = iPr2 NEtPDI or Me2NPrPDI). The investigation of (iPr2NEtPDI)RhCl and ( Me2NPrPDI)RhCl by single-crystal X-ray diffraction verified the absence of amine arm coordination and a pseudo square-planar geometry about rhodium. Replacement of the chloride ligand with an outer-sphere anion was achieved by adding AgBF4 directly to ( iPr2NEtPDI)RhCl to form [(iPr 2NEtPDI)Rh][BF4]. Alternatively, this complex was prepared by chelate addition following the salt metathesis reaction between AgBF4 and [(COD)RhCl]2. Using the latter method, both [(NPDI)Rh][BF4] complexes were isolated and found to exhibit κ4-N,N,N,N-PDI coordination regardless of arm length or steric bulk. In contrast, the metallation of PPDI chelates featuring alkylphosphane imine substituents (PPDI = Ph 2PEtPDI or Ph2PPrPDI) resulted in the formation of cationic complexes featuring κ5-N, N,N,P,P-PDI coordination in all instances, [(PPDI)Rh][X] (X = Cl, BF4). Adjusting the metallation stoichiometry allowed the preparation of [(Ph2PPrPDI)Rh][(COD)RhCl2], as validated by multinuclear NMR spectroscopy and single-crystal X-ray diffraction. The coordinative flexibility of newly prepared PDI ligands has been evaluated following their addition to [(COD)RhCl]2. Tailoring this chelate class to include donor atoms has allowed the preparation of complexes featuring tetradentate and pentadentate PDI coordination.
Original language | English (US) |
---|---|
Pages (from-to) | 4430-4442 |
Number of pages | 13 |
Journal | European Journal of Inorganic Chemistry |
Issue number | 25 |
DOIs | |
State | Published - Sep 2013 |
Keywords
- Coordination modes
- Electronic structure
- Ligand design
- Non-innocent ligands
- Rhodium
ASJC Scopus subject areas
- Inorganic Chemistry
Fingerprint
Dive into the research topics of 'Rational design of rhodium complexes featuring κ4-N,N,N,N- and κ5-N,N,N,P,P-Bis(imino)pyridine ligands'. Together they form a unique fingerprint.Datasets
-
CCDC 926031: Experimental Crystal Structure Determination
Ben-Daat, H. (Creator), Hall, G. B. (Creator), Groy, T. L. (Creator) & Trovitch, R. (Creator), The Cambridge Structural Database, 2013
DOI: 10.5517/cc102lzn, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc102lzn&sid=DataCite
Dataset
-
CCDC 926030: Experimental Crystal Structure Determination
Ben-Daat, H. (Creator), Hall, G. B. (Creator), Groy, T. L. (Creator) & Trovitch, R. (Creator), The Cambridge Structural Database, 2013
DOI: 10.5517/cc102lym, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc102lym&sid=DataCite
Dataset
-
CCDC 926033: Experimental Crystal Structure Determination
Ben-Daat, H. (Creator), Hall, G. B. (Creator), Groy, T. L. (Creator) & Trovitch, R. (Creator), The Cambridge Structural Database, 2013
DOI: 10.5517/cc102m1r, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/cc102m1r&sid=DataCite
Dataset