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Synthesis and structural dynamics of five-coordinate Rh(III) and Ir(III) PNP and PONOP pincer complexes
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Hood, Thomas M., Leforestier, Baptiste, Gyton, Matthew R. and Chaplin, Adrian B. (2019) Synthesis and structural dynamics of five-coordinate Rh(III) and Ir(III) PNP and PONOP pincer complexes. Inorganic Chemistry, 58 (11). pp. 7593-7601. doi:10.1021/acs.inorgchem.9b00957 ISSN 0020-1669.
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Official URL: https://doi.org/10.1021/acs.inorgchem.9b00957
Abstract
The synthesis and characterization of a homologous series of five-coordinate rhodium(III) and iridium(III) complexes of the PNP (2,6-(tBu2PCH2)2C5H3N) and PONOP (2,6-(tBu2PO)2C5H3N) pincer ligands are described: [M(PNP)(biph)][BArF4] (M = Rh, 1a; Ir, 1b; biph = 2,2’-biphenyl; ArF = 3,5-(CF3)2C6H3) and [M(PONOP)(biph)][BArF4] (M = Rh, 2a; Ir, 2b). These complexes are structurally dynamic in solution, exhibiting pseudorotation of the biph ligand on the 1H NMR timescale (ΔG‡ ca. 60 kJmol-1) and, in the case of the flexible PNP complexes, undergoing interconversion between helical and puckered pincer ligand conformations (ΔG‡ ca. 10 kJmol-1). Remarkably, the latter is sufficiently facile that it persists in the solid state, leading to temperaturedependent disorder in the associated X-ray crystal structures. Reaction of 1 and 2 with CO occurs for the iridium congeners 1b and 2b, leading to the formation of sterically congested carbonyl derivatives.
Item Type: | Journal Article | ||||||||||||||||||
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Subjects: | Q Science > QD Chemistry T Technology > TA Engineering (General). Civil engineering (General) |
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Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||||||||||||
Library of Congress Subject Headings (LCSH): | Structural dynamics , Ligands (Biochemistry) , Chemistry, Inorganic | ||||||||||||||||||
Journal or Publication Title: | Inorganic Chemistry | ||||||||||||||||||
Publisher: | American Chemical Society | ||||||||||||||||||
ISSN: | 0020-1669 | ||||||||||||||||||
Official Date: | 22 May 2019 | ||||||||||||||||||
Dates: |
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Volume: | 58 | ||||||||||||||||||
Number: | 11 | ||||||||||||||||||
Page Range: | pp. 7593-7601 | ||||||||||||||||||
DOI: | 10.1021/acs.inorgchem.9b00957 | ||||||||||||||||||
Status: | Peer Reviewed | ||||||||||||||||||
Publication Status: | Published | ||||||||||||||||||
Access rights to Published version: | Restricted or Subscription Access | ||||||||||||||||||
Date of first compliant deposit: | 16 May 2019 | ||||||||||||||||||
Date of first compliant Open Access: | 25 June 2019 | ||||||||||||||||||
RIOXX Funder/Project Grant: |
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