Fine tuning of reactivity and structure of bis(σ)borate and borate complexes of manganese by systematic ligand variation

Abstract : The complexes with fac-[M(CO)3]+ units of group-7 metals are interesting synthons for the development of target-specific drugs. Therefore, thermolysis reaction of Re2(CO)10 with various borate ligands have been investigated as a possible route to isolate bis(σ)borate complexes of rhenium. The reaction of trihydrobis(benzothiazol-2-yl)amideborate, Na[(H3B)bbza](bbza = bis(benzothiazol-2-yl)amine)with Re2(CO)10 led to the formation of distorted octahedral rhenium complexes [(CO)2Re{N(C7H4NS)2}2], 1 and [(CO)2Re{N(C7H4NS)2}{C6H4N(Me)O}], 2. In order to increase the library of complexes containing fac-{M(CO)3}+ moieties as well as to check the lability of the metal–carbonyl bond, reactivity of manganese borate complexes [Mn(CO)3(μ-H)2BHNCSC6H4(NR)], 3 (R = NCSC6H4)and [Mn(CO)3{κ3-S,S′,H-H2B(mbz)2}], 6 (mbz = 2-mercapto-benzothiazolyl)with different ligands were carried out. Photolysis of 3 with excess phosphine ligands (PPh2Me or PMe2Ph)yielded manganese phosphine complexes [Mn(CO)2(PL2L′)2{N(C7H4NS)2}], (4a L = Ph, L′ = Me; 4b L = Me, L′ = Ph). Interestingly, the reaction of 3 with tBuNC yielded mono/bis(tBuNC)-substituted manganese borate complexes [Mn(μ-H)2(BHNCSC6H4)(NR)(CO)xLy], 5a–b (5a x = 2, y = 1; 5b x = 1; y = 2; L = tBuNC; R = NCSC6H4)and [Mn(μ-H)2BH{N(NCSC6H4)2}(CO)(tBuNC)2], 5c. Compounds 5b and 5c are structural isomers with a different coordination mode of the bbza ligand. Under similar reaction conditions, photolysis of 6 with PPh3 in toluene generated borate complex of manganese [Mn(CO2){κ3-S,S′,H-H2B(mbz)2}(PPh3)], 7. All the compounds were characterised by multi-nuclear NMR, IR spectroscopy and mass spectrometry. Density functional theory (DFT)calculations were carried out to investigate the bonding and electronic structures of these compounds.
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C. Nandi, K. Saha, S. Gomosta, V. Dorcet, S. Ghosh. Fine tuning of reactivity and structure of bis(σ)borate and borate complexes of manganese by systematic ligand variation. Polyhedron, Elsevier, In press, ⟨10.1016/j.poly.2019.04.041⟩. ⟨hal-02161850⟩

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