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Various rhodium(I) pincer complexes with different structural features have been prepared and found to display interesting self-assembly properties due to the extensive Rh(I)···Rh(I) interactions. The incorporation of electron-withdrawing -CF substituent has been found to improve the stability of the complexes and also facilitate the directed assembly of complex molecules, providing an opportunity for the systematic investigation of the various noncovalent interactions in their versatile self-assembly behaviors and insights into the structure-property relationship in governing the intermolecular interactions. An isodesmic growth mechanism is identified for the solvent-induced aggregation process. The complex molecules exhibit intense low-energy absorption bands corresponding to the absorptions of the dimers, trimers, and higher order oligomers upon aggregation, with energies related to the electronic properties of the tridentate N-donor ligand. Chiral auxiliaries have also been introduced into the rhodium(I) complexes to build up helical supramolecular assemblies and soft materials.
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http://dx.doi.org/10.1021/jacs.8b04687 | DOI Listing |
Chemistry
July 2024
Humboldt-Universität zu Berlin, Department of Chemistry, Brook-Taylor-Straße 2, 12489, Berlin, Germany.
The κ-(P,N)-phosphine ligand precursor NH(CHCHPCy) can be used for the synthesis of the rhodium(I) complex [Rh(CO){ĸ-(P,N,P)-CyPCHNHCHPCy}][Cl] (1). The deprotonated complex [Rh(CO){ĸ-(P,N,P)-CyPCHNCHPCy}] (2) shows a cooperative reactivity of the PNP ligand in the activation reaction of SOF to yield the rhodium fluorido complex trans-[Rh(F)(CO){ĸ-(P,P)-CyPCHN(SOF)CHPCy}] (3) by S-F bond cleavage. It is remarkable that no reaction was observed when 3 was treated with hydrogen sources e.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2023
Institute of Advanced Materials (INAM), Universitat Jaume I, Av. Vicente Sos Baynat s/n., Castellón, E-12071, Spain.
We report the rhodium(I) complex [Rh(CNC-NDI)(CO)] , in which CNC-NDI refers to a pincer-CNC ligand decorated with a naphthalenediimide moiety. Due to the presence of the planar CNC ligand and the naphthalenediimide moiety, the electronic nature of the complex can be modulated by means of supramolecular and redox stimuli, respectively. The metal complex shows a strong π-π-stacking interaction with coronene.
View Article and Find Full Text PDFOrganometallics
December 2022
Department of Chemistry, University of Warwick, Gibbet Hill Road, CoventryCV4 7AL, U.K.
Chemistry
August 2022
Centro de Innovación en Química Avanzada (ORFEO-CINQA), Departamento de Química Orgánica e Inorgánica, Universidad de Oviedo, 33071, Oviedo, Spain.
A family of germyl rhodium complexes derived from the PGeP germylene 2,2'-bis(di-isopropylphosphanylmethyl)-5,5'-dimethyldipyrromethane-1,1'-diylgermanium(II), Ge(pyrmP Pr ) CMe (1), has been prepared. Germylene 1 reacted readily with [RhCl(PPh ) ] and [RhCl(cod)(PPh )] (cod=1,5-cyclooctadiene) to give, in both cases, the PGeP-pincer chloridogermyl rhodium(I) derivative [Rh{κ P,Ge,P-GeCl(pyrmP Pr ) CMe }(PPh )] (2). Similarly, the reaction of 1 with [RhCl(cod)(MeCN)] afforded [Rh{κ P,Ge,P-GeCl(pyrmP Pr ) CMe }(MeCN)] (3).
View Article and Find Full Text PDFThe synthesis and organometallic chemistry of rhodium(I) complex [Rh(CNC-Me)(SOMe)][BAr ], featuring NHC-based pincer and labile dimethyl sulfoxide ligands, is reported. This complex reacts with biphenylene and chlorobenzene to afford products resulting from selective C-C and C-Cl bond activation, [Rh(CNC-Me)(2,2'-biphenyl)(OSMe)][BAr ] and [Rh(CNC-Me)(Ph)Cl(OSMe)][BAr ], respectively. A detailed DFT-based computational analysis indicates that C-H bond oxidative addition of these substrates is kinetically competitive, but in all cases endergonic: contrasting the large thermodynamic driving force calculated for insertion of the metal into the C-C and C-Cl bonds, respectively.
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