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1H and 13C NMR assignments with coordination-induced shift calculations of carbon σ-bonded ortho-metalated rhodium(III) and iridium(III) complexes

✍ Scribed by Fred O. Garces; Richard J. Watts

Publisher
John Wiley and Sons
Year
1993
Tongue
English
Weight
807 KB
Volume
31
Category
Article
ISSN
0749-1581

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✦ Synopsis

Abstract

Complete ^1^H and ^13^C NMR assignments and coordination‐induced shift [CIS, δ~(complex)~ – δ~(free ligand)~] calculations for carbon σ‐bonded ortho‐metalated rhodium(III) and iridium(III) complexes are described. NMR parameters are used as probes of van der Waals interactions and ring current anisotropy in the ligand's environmental framework and to monitor σ‐donation and π‐back‐bonding within the ligand in this family of ortho‐metalated complexes. CIS measurements indicate large charge redistribution within the ligands as a result of ortho‐metalation to the rhodium(III) or iridium(III) cationic metal centers. The pulse sequences, attached proton test (APT), ^1^H^1^H homonuclear correlation spectroscopy (COSY), single‐frequency off‐resonance decoupling (SFORD) and ^1^H^13^C heteronuclear correlation spectroscopy (HETCOR), were utilized to assign all proton and carbon resonances of [Rh(ppy)~2~Cl]~2~, [Ir(ppy)~2~Cl]~2~, [Ir(ptpy)~2~Cl]~2~, [Ir(mppy)~2~Cl]~2~, [Rh(ppy)~2~bpy]^+^, [Ir(ppy)~2~bpy]^+^, [Ir(ptpy)~2~bpy]^+^ and [Ir(mppy)~2~bpy]^+^, where ppy is 2‐phenylpyridine, ptpy is 2‐(p‐tolyl)pyridine, mppy is 3‐methyl‐2‐phenylpyridine and bpy is 2,2′‐bipyridine.

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