New heteronuclear bridged borylene complexes that were derived from [{Cp*CoCl}2] and mono-metal—carbonyl fragments

Sharmila, Dudekula ; Yuvaraj, K. ; Barik, Subrat Kumar ; Roy, Dipak Kumar ; Chakrahari, Kiran Kumarvarma ; Ramalakshmi, Rongala ; Mondal, Bijan ; Varghese, Babu ; Ghosh, Sundargopal (2013) New heteronuclear bridged borylene complexes that were derived from [{Cp*CoCl}2] and mono-metal—carbonyl fragments Chemistry - A European Journal, 19 (45). pp. 15219-15225. ISSN 0947-6539

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The synthesis, structural characterization, and reactivity of new bridged borylene complexes are reported. The reaction of [{Cp*CoCl}2] with LiBH4⋅THF at −70 °C, followed by treatment with [M(CO)3(MeCN)3] (M=W, Mo, and Cr) under mild conditions, yielded heteronuclear triply bridged borylene complexes, [(μ3-BH)(Cp*Co)2 (μ-CO)M(CO)5] (1–3; 1: M=W, 2: M=Mo, 3: M=Cr). During the syntheses of complexes 1–3, capped-octahedral cluster [(Cp*Co)2 (μ-H)(BH)4{Co(CO)2}] (4) was also isolated in good yield. Complexes 1–3 are isoelectronic and isostructural to [(μ3-BH)(Cp*RuCO)2 (μ-CO){Fe(CO)3}] (5) and [(μ3-BH)(Cp*RuCO)2(μ-H)(μ-CO){Mn(CO)3}] (6), with a trigonal-pyramidal geometry in which the μ3-BH ligand occupies the apical vertex. To test the reactivity of these borylene complexes towards bis-phosphine ligands, the room-temperature photolysis of complexes 1–3, 5, 6, and [{(μ3-BH)(Cp*Ru)Fe(CO)3}2(μ-CO)] (7) was carried out. Most of these complexes led to decomposition, although photolysis of complex 7 with [Ph2P(CH2)nPPh2] (n=1–3) yielded complexes 9–11, [3,4-(Ph2P(CH2)nPPh2)-closo-1,2,3,4-Ru2Fe2 (BH)2] (9: n=1, 10: n=2, 11: n=3). Quantum-chemical calculations by using DFT methods were carried out on compounds 1–3 and 9–11 and showed reasonable agreement with the experimentally obtained structural parameters, that is, large HOMO–LUMO gaps, in accordance with the high stabilities of these complexes, and NMR chemical shifts that accurately reflected the experimentally observed resonances. All of the new compounds were characterized in solution by using mass spectrometry, IR spectroscopy, and 1H, 13C, and 11B NMR spectroscopy and their structural types were unequivocally established by crystallographic analysis of complexes 1, 2, 4, 9, and 10.

Item Type:Article
Source:Copyright of this article belongs to John Wiley & Sons, Inc.
Keywords:Boron; Borylenes; Heterometallic Complexes; Thermolysis; Tungsten
ID Code:108851
Deposited On:31 Jan 2018 12:17
Last Modified:31 Jan 2018 12:17

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