Reactivity of the iridium nitrosyl complex [Ir(NO)(paa)(PPh3)2][PF6]2(paa = 2-pyridinecarbaldehyde azine) with nucleophiles: insertion of NO into a methinic C–H bond; crystal structure of [Ir{(2-C5H4N)CHN–NC(NOH)(2-C5H4N)}{Me-(EtO)CNH}(PPh3)2][PF6]2

Ruthenium complexes [(η5‐C5H5)Ru(PPh3)(κ2‐paa)]PF6 (paa = pyridine‐2‐carbaldehyde azine) and [(η5‐C5H5)Ru(κ1‐dppm)(κ2‐paa)]BF4 [dppm = bis(diphenylphosphanyl)methane] have been employed as a synthon in the synthesis of homo/hetero bi‐/trimetallic complexes. It is the uncoordinatedN,N‐donor site on paa in complex [(η5‐C5H5)Ru(PPh3)(κ2‐paa)]PF6, and N,N‐donor site on paa and pendant phosphorus in [(η5‐C5H5)Ru(κ1‐dppm)(κ2‐paa)]BF4 that allows for their incorporation into bi‐/trimetallic systems. The resulting complexes have been characterized by analytical, spectral and electrochemical studies. Molecular structures of homo‐bimetallic complex [(PPh3)(η5‐C5H5)Ru(μ‐paa)Ru(η6‐C10H14)Cl](PF6)2 and hetero‐bimetallic complex [(PPh3)(η5‐C5H5)Ru(μ‐paa)Rh(η5‐C5Me5)Cl](PF6)2 have been authenticated crystallographically. Complexes exhibit absorptions throughout the visible region and complicated electrochemical behaviour. Metal‐based RuII/RuIII oxidations in the bimetallic complexes do not vary as in the trimetallic complexes. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Iridium

Yellowlees

Macnamara

2003

Comprehensive Coordination Chemistry II

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Reactivity of the iridium nitrosyl complex [Ir(NO)(paa)(PPh₃)₂][PF₆]₂(paa = 2-pyridinecarbaldehyde azine) with nucleophiles: insertion of NO into a methinic C–H bond; crystal structure of [Ir{(2-C₅H₄N)CHN–NC(NOH)(2-C₅H₄N)}{Me-(EtO)CNH}(PPh₃)₂][PF₆]₂

Abstract: The title complex (I) reacts with nitriles such as (II) or Li salts (IV) with intramolecular insertion of the NO group into the methinic C‐H bond of the uncoordinated ligand fragment to give the cyclometalated compounds (III) and (V).

Cited by 10 publications

References 9 publications

ChemInform Abstract: Reactivity of the Iridium Nitrosyl Complex (Ir(NO)(paa)(PPh3)2) (PF6)2 (paa: 2‐Pyridinecarbaldehyde Azine) with Nucleophiles: Insertion of NO into a Methinic C‐H Bond; Crystal Structure of (Ir((2‐C5H4N)CH=N‐N=C(NOH)(2‐C5H4N))(Me(EtO)C=NH)(PPh3)2) (PF6)2.

ChemInform Abstract: Reactivity of the Iridium Nitrosyl Complex (Ir(NO)(paa)(PPh3)2) (PF6)2 (paa: 2‐Pyridinecarbaldehyde Azine) with Nucleophiles: Insertion of NO into a Methinic C‐H Bond; Crystal Structure of (Ir((2‐C5H4N)CH=N‐N=C(NOH)(2‐C5H4N))(Me(EtO)C=NH)(PPh3)2) (PF6)2.

Ruthenium Complexes Containing Pyridine‐2‐carbaldehyde Azine as a Synthon in the Synthesis of Bi‐/Trimetallic Complexes

Iridium

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