Complexes of transition metal carbonyl clusters with tin(ii) phthalocyanine in neutral and radical anion states: methods of synthesis, structures and properties. Issue 6 (19th January 2022)

• Record Type: Journal Article
• Authors: Romanenko, Nikita R.; Kuzmin, Alexey V.; Khasanov, Salavat S.; Faraonov, Maxim A.; Yudanova, Evgeniya I.; Nakano, Yoshiaki; Otsuka, Akihiro; Yamochi, Hideki; Kitagawa, Hiroshi; Konarev, Dmitri V.
• Is Part Of: Dalton transactions. Volume 51:Issue 6(2022)
• Page Start: 2226
• Page End: 2237
• Publication Date: 2022-01-19
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Chemistry, Inorganic -- Periodicals; 546.05
• DOI: 10.1039/d1dt04061h
• Languages: English
• ISSNs: 1477-9226

Abstract

Abstract : Transition metal carbonyl clusters (Co4 (CO)12, Ru3 (CO)12, Os3 (CO)12, Ir4 (CO)12 ) coordinate one or two tin(ii ) phthalocyanines in neutral or radical anion state. Crystal structures, optical and magnetic properties of the complexes are discussed. Abstract : Coordination of tin(ii ) phthalocyanine to transition metal carbonyl clusters in neutral {Sn II (Pc 2− )} 0 or radical anion {Sn II (Pc˙ 3− )} − states is reported. Direct interaction of Co4 (CO)12 with {Sn II (Pc 2− )} 0 yields a crystalline complex {Co4 (CO)11 ·Sn II (Pc 2− )} (1 ). There is no charge transfer from the cluster to phthalocyanine in 1, which preserves the diamagnetic Pc 2− macrocycle. The Ru3 (CO)12 cluster forms complexes with one or two equivalents of {Sn II (Pc˙ 3− )} − to yield crystalline {Cryptand[2.2.2](Na + )}{Ru3 (CO)11 ·Sn II (Pc˙ 3− )} − (2 ) or {Cryptand[2.2.2](M + )}2 {Ru3 (CO)10 ·[Sn II (Pc˙ 3− )]2 } 2− ·4C6 H4 Cl2 (3 ) (M + is K or Cs). Paramagnetic {Sn II (Pc˙ 3− )} − species in 2 are packed in π -stacking [{Sn II (Pc˙ 3− )} − ]2 dimers, providing strong antiferromagnetic coupling of spins with exchange interaction J / k B = −19 K. Reduction of Ru3 (CO)12, Os3 (CO)12 and Ir4 (CO)12 clusters by decamethylchromocene (Cp*2 Cr) and subsequent oxidation of the reduced species by {Sn IV Cl2 (Pc 2− )} 0 yield a series of complexes with high-spin Cp*2 Cr + counter cations ( S = 3/2): (Cp*2 Cr + ){Ru3 (CO)11 ·Sn II (Pc˙ 3− )} − ·C6 H4 Cl2 (4 ), (Cp*2 Cr + ){Os3 (CO)10 Cl·Sn II (Pc˙ 3− )} − ·C6 H4 Cl2 (5 ) and (Cp*2 Cr + ){Ir4 (CO)11 ·Sn II (Pc˙ 3− )}2 − (6 ). It is seen that reduced clusters are oxidized by Sn IV, which is transferred to Sn II, whereas the Pc 2− macrocycle is reduced to Pc˙ 3− . In the case of Os3 (CO)12, oxidation of the metal atom in the cluster is observed to be accompanied by the formation of Os3 (CO)10 Cl with one Os I center. Rather weak magnetic coupling is observed between paramagnetic Cp*2 Cr + and {Sn II (Pc˙ 3− )} − species in 4, but this exchange interaction is enhanced in 5 owing to Os3 (CO)10 Cl clusters with paramagnetic Os I ( S = 1/2) also being involved in antiferromagnetic coupling of spins. The formation of {Sn II (Pc˙ 3− )} − with radical trianion Pc˙ 3− macrocycles in 2–5 is supported by the appearance of new absorption bands in the NIR spectra and essential Nmeso –C bond alternation in Pc (for 3–5 ). On the whole, this work shows that both diamagnetic {Sn II (Pc 2− )} 0 and paramagnetic {Sn II (Pc˙ 3− )} − ligands substitute carbonyl ligands in the transition metal carbonyl clusters, forming well-soluble paramagnetic solids absorbing light in the visible and NIR ranges.